Aromatic urea derivatives and their use as herbicide

ABSTRACT

PCT No. PCT/JP86/00398 Sec. 371 Date Apr. 1, 1987 Sec. 102(e) Date Apr. 1, 1987 PCT Filed Aug. 4, 1986 PCT Pub. No. WO87/00840 PCT Pub. Date Feb. 12, 1987.This invention relates to novel compounds of formula [I], a process for their production, and their use as a herbicide.   &lt;IMAGE&gt; [I]  wherein A represents the bond  &lt;IMAGE&gt;   in which X is a hydrogen atom, a chlorine atom, a nitro group or a trifluoromethyl group; B represents a hydrogen atom, a methyl group or a methoxy group; and Ar represents one member selected from the group consisting of  &lt;IMAGE&gt;  &lt;IMAGE&gt;  &lt;IMAGE&gt;  &lt;IMAGE&gt;  &lt;IMAGE&gt; +TR &lt;IMAGE&gt;    in which R1 to R38, are as defined hereinafter.

TECHNOLOGICAL FIELD

This invention relates to novel urea derivatives having herbicidalactivity and being useful as a herbicide, processes for productionthereof and a herbicide comprising such a urea derivative.

BACKGROUND TECHNOLOGY

Wheat, corn, rice and soybean are important crops, and many herbicideshave been used to increase the harvest of these crops. Conventionalherbicides, however, have not proved to be entirely satisfactory inregard to herbicidal activity or safety on crops, and it has beendesired to develop herbicides which kill hazardous weeds in low dosagesand do not cause phytotoxicity to crops.

It is an object of this invention to provide herbicidally active ureaderivatives which are not described in the prior literature and can meetthe aforesaid desire, processes for production thereof, a herbicidecomprising such a urea derivative as an active ingredient, and a methodof controlling weeds.

DISCLOSURE OF THE INVENTION

The present inventors have made investigations in order to develop aherbicidally active compound which is not likely to cause unnegligiblephytotoxicity to useful crops and can control hazardous weeds in lowdosages. These investigations have led to the successful synthesis ofurea derivatives represented by the following formula [I] not describedin the prior literature, and also to the discovery that the compounds offormula [I] are useful for controlling hazardous weeds at reduceddosages, have low phytotoxicity on useful crops, and are very superiorcompounds in herbicide applications. ##STR4## wherein A represents thebond ##STR5## in which X is a hydrogen atom, a chlorine atom, a nitrogroup or a trifluoromethyl group;

B represents a hydrogen atom, a methyl group or a methoxy group; and

Ar represents one member selected from the group consisting of ##STR6##in which R¹ to R³⁸, independently from each other, represent a hydrogenatom, a lower alkyl group or a lower alkoxy group; R¹⁶ may furtherrepresent a hydroxyl group; a pair of R² and R³, and a pair of R⁶ and R⁷each, taken together, may represent an alkylene linkage and may form a5- or 6-membered ring together with the two adjacent carbon atoms towhich they are bonded; a pair of R⁹ and R¹⁰, taken together, mayrepresent an alkylene linkage and may form a 5- or 6-membered ringtogether with the carbon atom to which they are bonded; R¹¹ and R¹²,taken together, may form an ethylenedioxy linkage --O--(CH₂)₂ --O--, orR¹¹ and R¹⁵, taken together, may form an alkylene linkage and form a 5-or 6-membered ring together with the carbon atoms to which they arebonded, or R¹⁵ and R¹⁶, taken together, may represent an alkylenelinkage and form a 5- or 6-membered ring together with one carbon atomto which they are bonded, or R¹⁴ and R¹⁵, taken together, may form adichloromethylene linkage.

When in general formula [I], R¹ to R³⁸ represent a lower alkyl group ora lower alkoxy group, they usually contain 1 to 4 carbon atoms,preferably 1 to 3 carbon atoms. Specific examples include methyl, ethyl,n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, methoxy,ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy and sec-butoxygroups.

When R² and R³ are bonded to each other to form an alkylene group, thetotal number of carbon atoms of the alkylene group is usually 3 or 4.Examples of the alkylene group are --CH₂ --₃ and --CH₂ --₄.

When R⁶ and R⁷ are bonded to each other to form an alkylene group, thetotal number of carbon atoms of the alkylene group are usually 3 to 5.Examples include ##STR7##

When R⁹ and R¹⁰ are bonded to each other to form an alkylene group, thetotal number of carbon atoms of the alkylene group is usually 4 or 5.Examples include --CH₂ --₄ and --CH₂ --₅.

When R¹¹ and R¹⁵ are bonded to each other to form an alkylene group, thetotal number of carbon atoms of the alkylene group is usually 2 or 3.Examples include --CH₂ --₂ and --CH₂ --₃.

When R¹⁵ and R¹⁶ are bonded to each other to form an alkylene group, thetotal number of carbon atoms is usually 4 or 5. Examples include --CH₂--₄ and --CH₂ --₅.

Examples of the Ar group are listed below. ##STR8##

Among these urea derivatives of this invention, preferred specificexamples are shown in Tables 1 to 11.

                  TABLE 1                                                         ______________________________________                                         ##STR9##                                                                      No.poundCom-                                                                        R.sup.1                                                                               R.sup.2                                                                              R.sup.3                                                                             R.sup.4                                                                             ##STR10##                                                                               B                                 ______________________________________                                         1    CH.sub.3                                                                              H      H     H                                                                                    ##STR11##                                                                              CH.sub.3                            2    CH.sub.3                                                                              H      H     H                                                                                    ##STR12##                                                                              OCH.sub.3                           3    CH.sub.3                                                                              H      H     H                                                                                    ##STR13##                                                                              H                                   4    CH.sub.3                                                                              H      H     H                                                                                    ##STR14##                                                                              CH.sub.3                            5    CH.sub.3                                                                              H      H     H                                                                                    ##STR15##                                                                              OCH.sub.3                           6    CH.sub.3                                                                              H      CH.sub.3                                                                            CH.sub.3                                                                             ##STR16##                                                                              CH.sub.3                            7    CH.sub.3                                                                              H      CH.sub.3                                                                            CH.sub.3                                                                             ##STR17##                                                                              OCH.sub.3                           8    CH.sub.3                                                                              H      CH.sub.3                                                                            CH.sub.3                                                                             ##STR18##                                                                              H                                   9    CH.sub.3                                                                              H      CH.sub.3                                                                            CH.sub.3                                                                             ##STR19##                                                                              CH.sub.3                           10    CH.sub.3                                                                              H      CH.sub.3                                                                            CH.sub.3                                                                             ##STR20##                                                                              OCH.sub.3                          11    H       H      H     H                                                                                    ##STR21##                                                                              CH.sub.3                           12    H       H      H     H                                                                                    ##STR22##                                                                              OCH.sub.3                          13    C.sub.2 H.sub.5                                                                       H      H     H                                                                                    ##STR23##                                                                              CH.sub.3                           14    C.sub.2 H.sub.5                                                                       H      H     H                                                                                    ##STR24##                                                                              OCH.sub.3                          15    .sup.n C.sub.3 H.sub.7                                                                H      H     H                                                                                    ##STR25##                                                                              CH.sub.3                           16    .sup.n C.sub.3 H.sub.7                                                                H      H     H                                                                                    ##STR26##                                                                              OCH.sub.3                          17    CH.sub.3                                                                              H      CH.sub. 3                                                                           H                                                                                    ##STR27##                                                                              CH.sub.3                           18    CH.sub.3                                                                              H      CH.sub.3                                                                            H                                                                                    ##STR28##                                                                              OCH.sub.3                          19    H       H      CH.sub.3                                                                            H                                                                                    ##STR29##                                                                              H                                  20    H       H      CH.sub.3                                                                            H                                                                                    ##STR30##                                                                              CH.sub.3                           21    H       H      CH.sub.3                                                                            H                                                                                    ##STR31##                                                                              OCH.sub.3                          22    H       H      C.sub.2 H.sub.5                                                                     H                                                                                    ##STR32##                                                                              H                                  23    H       H      C.sub.2 H.sub.5                                                                     H                                                                                    ##STR33##                                                                              CH.sub.3                           24    H       H      C.sub.2 H.sub.5                                                                     H                                                                                    ##STR34##                                                                              OCH.sub.3                          25    H       H      .sup.i C.sub.3 H.sub.7                                                              H                                                                                    ##STR35##                                                                              H                                  26    H       H      .sup.i C.sub.3 H.sub.7                                                              H                                                                                    ##STR36##                                                                              CH.sub.3                           27    H       H      .sup.i C.sub.3 H.sub.7                                                              H                                                                                    ##STR37##                                                                              OCH.sub.3                          28    H       H      .sup.s C.sub.4 H.sub.9                                                              H                                                                                    ##STR38##                                                                              H                                  29    H       H      .sup.s C.sub.4 H.sub.9                                                              H                                                                                    ##STR39##                                                                              CH.sub.3                           30    H       H      .sup.s C.sub.4 H.sub.9                                                              H                                                                                    ##STR40##                                                                              OCH.sub.3                          31    H       H      CH.sub.3                                                                            CH.sub.3                                                                             ##STR41##                                                                              H                                  32    H       H      CH.sub.3                                                                            CH.sub.3                                                                             ##STR42##                                                                              CH.sub.3                           33    H       H      CH.sub.3                                                                            CH.sub.3                                                                             ##STR43##                                                                              OCH.sub.3                          34    H       H      CH.sub.3                                                                            C.sub.2 H.sub.5                                                                      ##STR44##                                                                              H                                  35    H       H      CH.sub.3                                                                            C.sub.2 H.sub.5                                                                      ##STR45##                                                                              CH.sub.3                           36    H       H      CH.sub.3                                                                            C.sub.2 H.sub.5                                                                      ##STR46##                                                                              OCH.sub.3                          37    H       H      C.sub.2 H.sub.5                                                                     C.sub.2 H.sub.5                                                                      ##STR47##                                                                              H                                  38    H       H      C.sub.2 H.sub.5                                                                     C.sub.2 H.sub.5                                                                      ##STR48##                                                                              CH.sub.3                           39    H       H      C.sub.2 H.sub.5                                                                     C.sub.2 H.sub.5                                                                      ##STR49##                                                                              OCH.sub.3                          40    CH.sub.3                                                                              H      CH.sub.3                                                                            C.sub.2 H.sub.5                                                                      ##STR50##                                                                              H                                  41    CH.sub.3                                                                              H      CH.sub.3                                                                            C.sub.2 H.sub.5                                                                      ##STR51##                                                                              CH.sub.3                           42    CH.sub.3                                                                              H      CH.sub.3                                                                            C.sub.2 H.sub.5                                                                      ##STR52##                                                                              OCH.sub.3                          43    CH.sub.3                                                                              H      CH.sub.3                                                                            C.sub.2 H.sub.5                                                                      ##STR53##                                                                              CH.sub.3                           44    CH.sub.3                                                                              H      CH.sub.3                                                                            C.sub.2 H.sub.5                                                                      ##STR54##                                                                              OCH.sub.3                          45    CH.sub.3                                                                              H      CH.sub.3                                                                            C.sub.2 H.sub.5                                                                      ##STR55##                                                                              H                                  46    CH.sub.3                                                                              H      CH.sub.3                                                                            C.sub.2 H.sub.5                                                                      ##STR56##                                                                              CH.sub.3                           47    CH.sub.3                                                                              H      CH.sub.3                                                                            C.sub.2 H.sub.5                                                                      ##STR57##                                                                              OCH.sub.3                          48    CH.sub.3                                                                              H      CH.sub.3                                                                            C.sub.2 H.sub.5                                                                      ##STR58##                                                                              H                                  49    CH.sub.3                                                                              H      CH.sub.3                                                                            C.sub.2 H.sub.5                                                                      ##STR59##                                                                              CH.sub.3                           50    CH.sub.3                                                                              H      CH.sub.3                                                                            C.sub.2 H.sub.5                                                                      ##STR60##                                                                              OCH.sub.3                          51    CH.sub.3                                                                              H      CH.sub.3                                                                            C.sub.2 H.sub.5                                                                      ##STR61##                                                                              H                                  52    CH.sub.3                                                                              H      CH.sub.3                                                                            C.sub.2 H.sub.5                                                                      ##STR62##                                                                              CH.sub.3                           53    CH.sub.3                                                                              H      CH.sub.3                                                                            C.sub.2 H.sub.5                                                                      ##STR63##                                                                              OCH.sub.3                          54    C.sub.2 H.sub.5                                                                       H      CH.sub.3                                                                            CH.sub.3                                                                             ##STR64##                                                                              H                                  55    C.sub.2 H.sub.5                                                                       H      CH.sub.3                                                                            CH.sub.3                                                                             ##STR65##                                                                              CH.sub.3                           56    C.sub.2 H.sub.5                                                                       H      CH.sub.3                                                                            CH.sub.3                                                                             ##STR66##                                                                              OCH.sub.3                          57    H       (CH.sub.2).sub.4                                                                         CH.sub.3                                                                             ##STR67##                                                                              CH.sub.3                             58    H       (CH.sub.2).sub.4                                                                         CH.sub.3                                                                             ##STR68##                                                                              OCH.sub.3                            ______________________________________                                    

                                      TABLE 2                                     __________________________________________________________________________     ##STR69##                                                                     Compound No.                                                                          R.sup.5                                                                           R.sup.6                                                                            R.sup.7                                                                             R.sup.8                                                                          ##STR70##                                                                              B                                         __________________________________________________________________________    59      CH.sub.3                                                                          H    H     H                                                                                 ##STR71##                                                                             CH.sub.3                                   60      CH.sub.3                                                                          H    H     H                                                                                 ##STR72##                                                                             OCH.sub.3                                  61      CH.sub.3                                                                          H    H     H                                                                                 ##STR73##                                                                             CH.sub.3                                   62      CH.sub.3                                                                          H    H     H                                                                                 ##STR74##                                                                             OCH.sub.3                                  63      H   H    CH.sub.3                                                                            H                                                                                 ##STR75##                                                                             CH.sub.3                                   64       H  H    CH.sub.3                                                                            H                                                                                 ##STR76##                                                                             OCH.sub.3                                  65      H   H    C.sub.2 H.sub.5                                                                     H                                                                                 ##STR77##                                                                             CH.sub.3                                   66      H   H    C.sub.2 H.sub.5                                                                     H                                                                                 ##STR78##                                                                             OCH.sub.3                                  67      H   H    .sup.n C.sub.3 H.sub.7                                                              H                                                                                 ##STR79##                                                                             CH.sub.3                                   68      H   H    .sup.n C.sub.3 H.sub.7                                                              H                                                                                 ##STR80##                                                                             OCH.sub.3                                  69      H   H    .sup.i C.sub.3 H.sub.7                                                              H                                                                                 ##STR81##                                                                             H                                          70      H   H    .sup.i C.sub.3 H.sub.7                                                              H                                                                                 ##STR82##                                                                             CH.sub.3                                   71      H   H    .sup.i C.sub.3 H.sub.7                                                              H                                                                                 ##STR83##                                                                             OCH.sub.3                                  72      .sup.i C.sub.4 H.sub.9                                                            H    H     H                                                                                 ##STR84##                                                                             H                                          73      .sup.i C.sub.4 H.sub.9                                                            H    H     H                                                                                 ##STR85##                                                                             CH.sub.3                                   74      .sup.i C.sub.4 H.sub.9                                                            H    H     H                                                                                 ##STR86##                                                                             OCH.sub.3                                  75      OCH.sub.3                                                                         H    C.sub.2 H.sub. 5                                                                    H                                                                                 ##STR87##                                                                             H                                          76      OCH.sub.3                                                                         H    C.sub.2 H.sub.5                                                                     H                                                                                 ##STR88##                                                                             CH.sub.3                                   77      OCH.sub.3                                                                         H    C.sub.2 H.sub.5                                                                     H                                                                                 ##STR89##                                                                             OCH.sub.3                                  78      CH.sub.3                                                                          H    CH.sub.3                                                                            H                                                                                 ##STR90##                                                                             CH.sub.3                                   79      CH.sub.3                                                                          H    CH.sub.3                                                                            H                                                                                 ##STR91##                                                                             OCH.sub.3                                  80      CH.sub.3                                                                          H    CH.sub.3                                                                            H                                                                                 ##STR92##                                                                             H                                          81      CH.sub.3                                                                          H    CH.sub.3                                                                            H                                                                                 ##STR93##                                                                             CH.sub.3                                   82      CH.sub.3                                                                          H    CH.sub.3                                                                            H                                                                                 ##STR94##                                                                             OCH.sub.3                                  83      CH.sub.3                                                                          CH.sub.3                                                                           H     H                                                                                 ##STR95##                                                                             CH.sub.3                                   84      CH.sub.3                                                                          CH.sub.3                                                                           H     H                                                                                 ##STR96##                                                                             OCH.sub.3                                  85      CH.sub.3                                                                          CH.sub.3                                                                           H     H                                                                                 ##STR97##                                                                             CH.sub.3                                   86      CH.sub.3                                                                          CH.sub. 3                                                                          H     H                                                                                 ##STR98##                                                                             OCH.sub.3                                  87      H   H    CH.sub.3                                                                            CH.sub.3                                                                          ##STR99##                                                                             H                                          88      H   H    CH.sub.3                                                                            CH.sub.3                                                                          ##STR100##                                                                            CH.sub.3                                   89      H   H    CH.sub.3                                                                            CH.sub.3                                                                          ##STR101##                                                                            OCH.sub.3                                  90      OC.sub.2 H.sub.5                                                                  H    CH.sub.3                                                                            H                                                                                 ##STR102##                                                                            CH.sub.3                                   91      OC.sub.2 H.sub.5                                                                  H    CH.sub.3                                                                            H                                                                                 ##STR103##                                                                            OCH.sub.3                                  92      OCH.sub.3                                                                         H    CH.sub.3                                                                            CH.sub.3                                                                          ##STR104##                                                                            CH.sub.3                                   93      OCH.sub.3                                                                         H    CH.sub.3                                                                            CH.sub.3                                                                          ##STR105##                                                                            OCH.sub.3                                  94      OCH.sub.3                                                                         H    CH.sub.3                                                                            CH.sub.3                                                                          ##STR106##                                                                            H                                          95      OCH.sub.3                                                                         H    CH.sub.3                                                                            CH.sub.3                                                                          ##STR107##                                                                            CH.sub.3                                   96      OCH.sub.3                                                                         H    CH.sub.3                                                                            CH.sub.3                                                                          ##STR108##                                                                            OCH.sub.3                                  97      OCH.sub.3                                                                         H    CH.sub.3                                                                            CH.sub.3                                                                          ##STR109##                                                                            CH.sub.3                                   98      OCH.sub.3                                                                         H    CH.sub.3                                                                            CH.sub.3                                                                          ##STR110##                                                                            OCH.sub.3                                  99      OCH.sub.3                                                                         H    CH.sub.3                                                                            C.sub.2 H.sub.5                                                                   ##STR111##                                                                            H                                          100     OCH.sub.3                                                                         H    CH.sub.3                                                                            C.sub.2 H.sub.5                                                                   ##STR112##                                                                            CH.sub.3                                   101     OCH.sub.3                                                                         H    CH.sub.3                                                                            C.sub.2 H.sub.5                                                                   ##STR113##                                                                            OCH.sub.3                                  102     OCH.sub.3                                                                         H    C.sub.2 H.sub.5                                                                     C.sub.2 H.sub.5                                                                   ##STR114##                                                                            H                                          103     OCH.sub.3                                                                         H    C.sub.2 H.sub.5                                                                     C.sub.2 H.sub.5                                                                   ##STR115##                                                                            CH.sub.3                                   104     OCH.sub.3                                                                         H    C.sub.2 H.sub.5                                                                     C.sub.2 H.sub.5                                                                   ##STR116##                                                                            OCH.sub.3                                  105     OCH.sub.3                                                                         H    iC.sub.3 H.sub.7                                                                    H                                                                                 ##STR117##                                                                            CH.sub.3                                   106     OCH.sub.3                                                                         H    iC.sub.3 H.sub.7                                                                    H                                                                                 ##STR118##                                                                            OCH.sub. 3                                 107     OC.sub.2 H.sub.5                                                                  H    C.sub.2 H.sub.5                                                                     H                                                                                 ##STR119##                                                                            CH.sub.3                                   108     OC.sub.2 H.sub.5                                                                  H    C.sub.2 H.sub.5                                                                     H                                                                                 ##STR120##                                                                            OCH.sub.3                                  109     OC.sub.2 H.sub.5                                                                  H    iC.sub.3 H.sub.7                                                                    H                                                                                 ##STR121##                                                                            H                                          110     OC.sub.2 H.sub.5                                                                  H    iC.sub.3 H.sub.7                                                                    H                                                                                 ##STR122##                                                                            CH.sub.3                                   111     OC.sub.2 H.sub.5                                                                  H    iC.sub.3 H.sub.7                                                                    H                                                                                 ##STR123##                                                                            OCH.sub.3                                  112     OC.sub.2 H.sub.5                                                                  H    CH.sub.3                                                                            CH.sub.3                                                                          ##STR124##                                                                            CH.sub.3                                   113     OC.sub.2 H.sub.5                                                                  H    CH.sub.3                                                                            CH.sub.3                                                                          ##STR125##                                                                            OCH.sub.3                                  114     OC.sub.3 H.sub.7 i                                                                H    CH.sub.3                                                                            CH.sub.3                                                                          ##STR126##                                                                            CH.sub.3                                   115     OC.sub.3 H.sub.7 i                                                                H    CH.sub.3                                                                            CH.sub.3                                                                          ##STR127##                                                                            OCH.sub.3                                  116     H   (CH.sub.2).sub.4                                                                         H                                                                                 ##STR128##                                                                            H                                          117     H   (CH.sub.2).sub.4                                                                         H                                                                                 ##STR129##                                                                            CH.sub.3                                   118     H   (CH.sub.2).sub.4                                                                         H                                                                                 ##STR130##                                                                            OCH.sub.3                                  119     H                                                                                  ##STR131##                                                                              H                                                                                 ##STR132##                                                                            H                                          120     H                                                                                  ##STR133##                                                                              H                                                                                 ##STR134##                                                                            CH.sub.3                                   121     H                                                                                  ##STR135##                                                                              H                                                                                 ##STR136##                                                                            OCH.sub.3                                  122     H                                                                                  ##STR137##                                                                              H                                                                                 ##STR138##                                                                            H                                          123     H                                                                                  ##STR139##                                                                              H                                                                                 ##STR140##                                                                            CH.sub.3                                   124     H                                                                                  ##STR141##                                                                              H                                                                                 ##STR142##                                                                            OCH.sub.3                                  __________________________________________________________________________

                  TABLE 3                                                         ______________________________________                                         ##STR143##                                                                    Compound No.                                                                            R.sup.9  R.sup.10                                                                               ##STR144##                                                                               B                                     ______________________________________                                        125       H        H                                                                                       ##STR145##                                                                              H                                      126       H        H                                                                                       ##STR146##                                                                              CH.sub.3                               127       H        H                                                                                       ##STR147##                                                                              OCH.sub.3                              128       C.sub.2 H.sub.5                                                                        CH.sub.3                                                                                ##STR148##                                                                              H                                      129       C.sub.2 H.sub.5                                                                        CH.sub.3                                                                                ##STR149##                                                                              CH.sub.3                               130       C.sub.2 H.sub.5                                                                        CH.sub.3                                                                                ##STR150##                                                                              OCH.sub.3                              131       CH.sub.3 CH.sub.3                                                                                ##STR151##                                                                              CH.sub. 3                              132       CH.sub.3 CH.sub.3                                                                                ##STR152##                                                                              OCH.sub.3                              133       CH.sub.3 CH.sub.3                                                                                ##STR153##                                                                              CH.sub.3                               134       CH.sub.3 CH.sub.3                                                                                ##STR154##                                                                              OCH.sub.3                              135       OCH.sub.3                                                                              CH.sub.3                                                                                ##STR155##                                                                              H                                      136       OCH.sub.3                                                                              CH.sub.3                                                                                ##STR156##                                                                              CH.sub.3                               137       OCH.sub.3                                                                              CH.sub.3                                                                                ##STR157##                                                                              OCH.sub.3                              138       OC.sub.2 H.sub.5                                                                       CH.sub.3                                                                                ##STR158##                                                                              CH.sub.3                               139       OC.sub.2 H.sub.5                                                                       CH.sub.3                                                                                ##STR159##                                                                              OCH.sub.3                              140       OC.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5                                                                         ##STR160##                                                                              CH.sub.3                               141       OC.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5                                                                         ##STR161##                                                                              OCH.sub.3                              142       OCH.sub.3                                                                              H                                                                                       ##STR162##                                                                              CH.sub.3                               143       OCH.sub.3                                                                              H                                                                                       ##STR163##                                                                              OCH.sub.3                              144       OC.sub.2 H.sub.5                                                                       H                                                                                       ##STR164##                                                                              CH.sub.3                               145       OC.sub.2 H.sub.5                                                                       H                                                                                       ##STR165##                                                                              OCH.sub.3                              146       CH.sub.3 .sup.i C.sub.3 H.sub.7                                                                  ##STR166##                                                                              H                                      147       CH.sub.3 .sup.i C.sub.3 H.sub.7                                                                  ##STR167##                                                                              CH.sub.3                               148       CH.sub.3 .sup.i C.sub.3 H.sub.7                                                                  ##STR168##                                                                              OCH.sub.3                              149       C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                         ##STR169##                                                                              H                                      150       C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                         ##STR170##                                                                              CH.sub.3                               151       C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                         ##STR171##                                                                              OCH.sub.3                              152       (CH.sub.2).sub.4                                                                             ##STR172##  H                                        153       (CH.sub.2).sub.4                                                                             ##STR173##  CH.sub.3                                 154       (CH.sub.2).sub. 4                                                                            ##STR174##  OCH.sub.3                                ______________________________________                                    

                                      TABLE 4                                     __________________________________________________________________________     ##STR175##                                                                    No.Compound                                                                         R.sup.11                                                                          R.sup.12                                                                          R.sup.13                                                                         R.sup.14                                                                        R.sup.15                                                                          R.sup.16                                                                            ##STR176##                                                                            B                                       __________________________________________________________________________    155   H   H   H  H H   H                                                                                    ##STR177##                                                                           CH.sub.3                                 156   H   H   H  H H   H                                                                                    ##STR178##                                                                           OCH.sub.3                                157   CH.sub.3                                                                          H   H  H H   H                                                                                    ##STR179##                                                                           CH.sub.3                                 158   CH.sub.3                                                                          H   H  H H   H                                                                                    ##STR180##                                                                           OCH.sub.3                                159   CH.sub.3                                                                          H   H  H H   H                                                                                    ##STR181##                                                                           CH.sub.3                                 160   CH.sub.3                                                                          H   H  H H   H                                                                                    ##STR182##                                                                           OCH.sub.3                                161   H   H   H  H CH.sub.3                                                                          H                                                                                    ##STR183##                                                                           CH.sub.3                                 162   H   H   H  H CH.sub.3                                                                          H                                                                                    ##STR184##                                                                           OCH.sub.3                                163   H   H   H  H CH.sub.3                                                                          H                                                                                    ##STR185##                                                                           H                                        164   H   H   H  H CH.sub.3                                                                          H                                                                                    ##STR186##                                                                           CH.sub.3                                 165   H   H   H  H CH.sub.3                                                                          H                                                                                    ##STR187##                                                                           OCH.sub.3                                166   CH.sub.3                                                                          CH.sub.3                                                                          H  H H   H                                                                                    ##STR188##                                                                           CH.sub.3                                 167   CH.sub.3                                                                          CH.sub.3                                                                          H  H H   H                                                                                    ##STR189##                                                                           OCH.sub.3                                168   H   H   H  H CH.sub.3                                                                          CH.sub.3                                                                             ##STR190##                                                                           H                                        169   H   H   H  H CH.sub.3                                                                          CH.sub.3                                                                             ##STR191##                                                                           CH.sub.3                                 170   H   H   H  H CH.sub.3                                                                          CH.sub.3                                                                             ##STR192##                                                                           OCH.sub.3                                171   H   H   H  H CH.sub.3                                                                          CH.sub.3                                                                             ##STR193##                                                                           H                                        172   H   H   H  H CH.sub.3                                                                          CH.sub.3                                                                             ##STR194##                                                                           CH.sub.3                                 173   H   H   H  H CH.sub.3                                                                          CH.sub.3                                                                             ##STR195##                                                                           OCH.sub.3                                174   H   H   H  H CH.sub.3                                                                          CH.sub.3                                                                             ##STR196##                                                                           CH.sub.3                                 175   H   H   H  H CH.sub.3                                                                          CH.sub.3                                                                             ##STR197##                                                                           OCH.sub.3                                176   H   H   H  H CH.sub.3                                                                          CH.sub.3                                                                             ##STR198##                                                                           CH.sub.3                                 177   H   H   H  H CH.sub.3                                                                          CH.sub.3                                                                             ##STR199##                                                                           OCH.sub.3                                178   H   H   H  H CH.sub.3                                                                          CH.sub.3                                                                             ##STR200##                                                                           CH.sub.3                                 179   H   H   H  H CH.sub.3                                                                          CH.sub.3                                                                             ##STR201##                                                                           OCH.sub.3                                180   CH.sub.3                                                                          CH.sub.3                                                                          H  H CH.sub.3                                                                          H                                                                                    ##STR202##                                                                           CH.sub.3                                 181   CH.sub.3                                                                          CH.sub.3                                                                          H  H CH.sub.3                                                                          H                                                                                    ##STR203##                                                                           OCH.sub.3                                182   CH.sub.3                                                                          CH.sub.3                                                                          H  H CH.sub.3                                                                          H                                                                                    ##STR204##                                                                           CH.sub.3                                 183   CH.sub.3                                                                          CH.sub.3                                                                          H  H CH.sub.3                                                                          H                                                                                    ##STR205##                                                                           OCH.sub.3                                184   CH.sub.3                                                                          H   H  H CH.sub.3                                                                          CH.sub.3                                                                             ##STR206##                                                                           OCH.sub.3                                185   CH.sub.3                                                                          H   H  H CH.sub.3                                                                          CH.sub.3                                                                             ##STR207##                                                                           CH.sub.3                                 186   CH.sub.3                                                                          H   H  H CH.sub.3                                                                          CH.sub.3                                                                             ##STR208##                                                                           OCH.sub.3                                187   OCH.sub.3                                                                         H   H  H CH.sub.3                                                                          CH.sub.3                                                                             ##STR209##                                                                           CH.sub.3                                 188   OCH.sub.3                                                                         H   H  H CH.sub.3                                                                          CH.sub.3                                                                             ##STR210##                                                                           OCH.sub.3                                189   CH.sub.3                                                                          CH.sub.3                                                                          H  H CH.sub.3                                                                          OCH.sub.3                                                                            ##STR211##                                                                           H                                        190   CH.sub.3                                                                          CH.sub.3                                                                          H  H CH.sub.3                                                                          OCH.sub.3                                                                            ##STR212##                                                                           CH.sub.3                                 191   CH.sub.3                                                                          CH.sub.3                                                                          H  H CH.sub.3                                                                          OCH.sub.3                                                                            ##STR213##                                                                           OCH.sub.3                                192   CH.sub.3                                                                          CH.sub.3                                                                          H  H CH.sub.3                                                                          OCH.sub.3                                                                            ##STR214##                                                                           H                                        193   CH.sub.3                                                                          CH.sub.3                                                                          H  H CH.sub.3                                                                          OCH.sub.3                                                                            ##STR215##                                                                           CH.sub.3                                 194   CH.sub.3                                                                          CH.sub.3                                                                          H  H CH.sub.3                                                                          OCH.sub.3                                                                            ##STR216##                                                                           OCH.sub.3                                195   CH.sub.3                                                                          CH.sub.3                                                                          H  H CH.sub.3                                                                          OCH.sub.3                                                                            ##STR217##                                                                           H                                        196   CH.sub.3                                                                          CH.sub.3                                                                          H  H CH.sub.3                                                                          OCH.sub.3                                                                            ##STR218##                                                                           CH.sub.3                                 197   CH.sub.3                                                                          CH.sub.3                                                                          H  H CH.sub.3                                                                          OCH.sub.3                                                                            ##STR219##                                                                           OCH.sub.3                                198   CH.sub.3                                                                          CH.sub.3                                                                          H  H CH.sub.3                                                                          OCH.sub.3                                                                            ##STR220##                                                                           H                                        199   CH.sub.3                                                                          CH.sub.3                                                                          H  H CH.sub.3                                                                          OCH.sub.3                                                                            ##STR221##                                                                           CH.sub.3                                 200   CH.sub.3                                                                          CH.sub.3                                                                          H  H CH.sub.3                                                                          OCH.sub.3                                                                            ##STR222##                                                                           OCH.sub.3                                201   CH.sub.3                                                                          CH.sub.3                                                                          H  H CH.sub.3                                                                          OCH.sub.3                                                                            ##STR223##                                                                           H                                        202   CH.sub.3                                                                          CH.sub.3                                                                          H  H CH.sub.3                                                                          OCH.sub.3                                                                            ##STR224##                                                                           CH.sub.3                                 203   CH.sub.3                                                                          CH.sub.3                                                                          H  H CH.sub.3                                                                          OCH.sub.3                                                                            ##STR225##                                                                           OCH.sub.3                                204   CH.sub.3                                                                          CH.sub.3                                                                          H  H CH.sub.3                                                                          OC.sub.2 H.sub.5                                                                     ##STR226##                                                                           CH.sub.3                                 205   CH.sub.3                                                                          CH.sub.3                                                                          H  H CH.sub.3                                                                          OC.sub.2 H.sub.5                                                                     ##STR227##                                                                           OCH.sub.3                                206   CH.sub.3                                                                          CH.sub.3                                                                          H  H CH.sub.3                                                                          OC.sub.3 H.sub.7n                                                                    ##STR228##                                                                           CH.sub.3                                 207   CH.sub.3                                                                          CH.sub.3                                                                          H  H CH.sub.3                                                                          OC.sub.3 H.sub.7n                                                                    ##STR229##                                                                           OCH.sub.3                                208   CH.sub.3                                                                          CH.sub.3                                                                          H  H CH.sub.3                                                                          OC.sub.3 H.sub.7i                                                                    ##STR230##                                                                           H                                        209   CH.sub.3                                                                          CH.sub.3                                                                          H  H CH.sub.3                                                                          OC.sub.3 H.sub.7i                                                                    ##STR231##                                                                           CH.sub.3                                 210   CH.sub.3                                                                          CH.sub.3                                                                          H  H CH.sub.3                                                                          OC.sub.3 H.sub.7i                                                                    ##STR232##                                                                           OCH.sub.3                                211   OCH.sub.3                                                                         H   H  H H   H                                                                                    ##STR233##                                                                           CH.sub.3                                 212   OCH.sub.3                                                                         H   H  H H   H                                                                                    ##STR234##                                                                           OCH.sub.3                                213   H   H   H  H C.sub.2 H.sub.5                                                                   H                                                                                    ##STR235##                                                                           CH.sub.3                                 214   H   H   H  H C.sub.2 H.sub.5                                                                   H                                                                                    ##STR236##                                                                           OCH.sub.3                                215   H   H   H  H .sup.i C.sub.3 H.sub.7                                                            H                                                                                    ##STR237##                                                                           H                                        216   H   H   H  H .sup.i C.sub.3 H.sub.7                                                            H                                                                                    ##STR238##                                                                           CH.sub.3                                 217   H   H   H  H .sup.i C.sub.3 H.sub.7                                                            H                                                                                    ##STR239##                                                                           OCH.sub.3                                218   H   H   H  H OCH.sub.3                                                                         H                                                                                    ##STR240##                                                                           H                                        219   H   H   H  H OCH.sub.3                                                                         H                                                                                    ##STR241##                                                                           CH.sub.3                                 220   H   H   H  H OCH.sub.3                                                                         H                                                                                    ##STR242##                                                                           OCH.sub.3                                221   H   H   H  H OC.sub.2 H.sub.5                                                                  H                                                                                    ##STR243##                                                                           CH.sub.3                                 222   H   H   H  H OC.sub.2 H.sub.5                                                                  H                                                                                    ##STR244##                                                                           OCH.sub.3                                223   C.sub.2 H.sub.5                                                                   H   H  H H   H                                                                                    ##STR245##                                                                           H                                        224   C.sub.2 H.sub.5                                                                   H   H  H H   H                                                                                    ##STR246##                                                                           CH.sub.3                                 225   C.sub.2 H.sub.5                                                                   H   H  H H   H                                                                                    ##STR247##                                                                           OCH.sub.3                                226   CH.sub.3                                                                          H   CH.sub.3                                                                         H H   H                                                                                    ##STR248##                                                                           H                                        227   CH.sub.3                                                                          H   CH.sub.3                                                                         H H   H                                                                                    ##STR249##                                                                           CH.sub.3                                 228   CH.sub.3                                                                          H   CH.sub.3                                                                         H H   H                                                                                    ##STR250##                                                                           OCH.sub.3                                229   CH.sub.3                                                                          H   H  H CH.sub.3                                                                          H                                                                                    ##STR251##                                                                           H                                        230   CH.sub.3                                                                          H   H  H CH.sub.3                                                                          H                                                                                    ##STR252##                                                                           CH.sub.3                                 231   CH.sub.3                                                                          H   H  H CH.sub.3                                                                          H                                                                                    ##STR253##                                                                           OCH.sub.3                                232   CH.sub.3                                                                          H   H  H OCH.sub.3                                                                         H                                                                                    ##STR254##                                                                           CH.sub.3                                 233   CH.sub.3                                                                          H   H  H OCH.sub.3                                                                         H                                                                                    ##STR255##                                                                           OCH.sub.3                                234   CH.sub.3                                                                          H   H  H OC.sub.2 H.sub.5                                                                  H                                                                                    ##STR256##                                                                           CH.sub.3                                 235   CH.sub.3                                                                          H   H  H OC.sub.2 H.sub.5                                                                  H                                                                                    ##STR257##                                                                           OCH.sub.3                                236   OCH.sub.3                                                                         H   H  H CH.sub.3                                                                          H                                                                                    ##STR258##                                                                           CH.sub.3                                 237   OCH.sub.3                                                                         H   H  H CH.sub.3                                                                          H                                                                                    ##STR259##                                                                           OCH.sub.3                                238   OCH.sub.3                                                                         H   H  H C.sub.2 H.sub.5                                                                   H                                                                                    ##STR260##                                                                           OCH.sub.3                                239   H   H   CH.sub.3                                                                         H CH.sub.3                                                                          H                                                                                    ##STR261##                                                                           CH.sub.3                                 240   H   H   CH.sub.3                                                                         H CH.sub.3                                                                          H                                                                                    ##STR262##                                                                           OCH.sub.3                                241   H   H   CH.sub.3                                                                         H C.sub.2 H.sub.5                                                                   H                                                                                    ##STR263##                                                                           CH.sub.3                                 242   H   H   CH.sub.3                                                                         H C.sub.2 H.sub.5                                                                   H                                                                                    ##STR264##                                                                           OCH.sub.3                                243   H   H   H  H CH.sub.3                                                                          C.sub.2 H.sub.5                                                                      ##STR265##                                                                           CH.sub.3                                 244   H   H   H  H CH.sub.3                                                                          C.sub.2 H.sub.5                                                                      ##STR266##                                                                           OCH.sub.3                                245   H   H   H  H CH.sub.3                                                                          .sup.n C.sub.3 H.sub.7                                                               ##STR267##                                                                           CH.sub.3                                 246   H   H   H  H CH.sub.3                                                                          .sup.n C.sub.3 H.sub.7                                                               ##STR268##                                                                           OCH.sub.3                                247   H   H   H  H CH.sub.3                                                                          .sup.i C.sub.3 H.sub.7                                                               ##STR269##                                                                           CH.sub.3                                 248   H   H   H  H CH.sub.3                                                                          .sup.i C.sub.3 H.sub.7                                                               ##STR270##                                                                           OCH.sub.3                                249   H   H   H  H C.sub.2 H.sub.5                                                                   C.sub.2 H.sub.5                                                                      ##STR271##                                                                           CH.sub.3                                 250   H   H   H  H C.sub.2 H.sub.5                                                                   C.sub.2 H.sub.5                                                                      ##STR272##                                                                           OCH.sub.3                                251   H   H   H  H C.sub.2 H.sub.5                                                                   .sup.n C.sub.3 H.sub.7                                                               ##STR273##                                                                           CH.sub.3                                 252   H   H   H  H C.sub.2 H.sub.5                                                                   .sup.n C.sub.3 H.sub.7                                                               ##STR274##                                                                           OCH.sub.3                                253   H   H   H  H (CH.sub.2).sub.5                                                                         ##STR275##                                                                           H                                        254   H   H   H  H (CH.sub.2).sub.5                                                                         ##STR276##                                                                           CH.sub.3                                 255   H   H   H  H (CH.sub.2).sub.5                                                                         ##STR277##                                                                           OCH.sub.3                                256   H   H   H  H CH.sub.3                                                                          OCH.sub.3                                                                            ##STR278##                                                                           H                                        257   H   H   H  H CH.sub.3                                                                          OCH.sub.3                                                                            ##STR279##                                                                           CH.sub.3                                 258   H   H   H  H CH.sub.3                                                                          OCH.sub.3                                                                            ##STR280##                                                                           OCH.sub.3                                259   H   H   H  H CH.sub.3                                                                          OC.sub.2 H.sub.3                                                                     ##STR281##                                                                           CH.sub.3                                 260   H   H   H  H CH.sub.3                                                                          OC.sub.2 H.sub.5                                                                     ##STR282##                                                                           OCH.sub.3                                261   H   H   H  H CH.sub.3                                                                          OC.sub.3 H.sub.7i                                                                    ##STR283##                                                                           CH.sub.3                                 262   H   H   H  H CH.sub.3                                                                          OC.sub.3 H.sub.7i                                                                    ##STR284##                                                                           OCH.sub.3                                263   H   H   H  H C.sub.2 H.sub.5                                                                   OCH.sub.3                                                                            ##STR285##                                                                           H                                        264   H   H   H  H C.sub.2 H.sub.5                                                                   OCH.sub.3                                                                            ##STR286##                                                                           CH.sub.3                                 265   H   H   H  H C.sub.2 H.sub.5                                                                   OCH.sub.3                                                                            ##STR287##                                                                           OCH.sub.3                                266   CH.sub.3                                                                          H   H  H CH.sub.3                                                                          OCH.sub.3                                                                            ##STR288##                                                                           H                                        267   CH.sub.3                                                                          H   H  H CH.sub.3                                                                          OCH.sub.3                                                                            ##STR289##                                                                           CH.sub.3                                 268   CH.sub.3                                                                          H   H  H CH.sub.3                                                                          OCH.sub.3                                                                            ##STR290##                                                                           OCH.sub.3                                269   CH.sub.3                                                                          H   H  H C.sub.2 H.sub.5                                                                   OCH.sub. 3                                                                           ##STR291##                                                                           H                                        270   CH.sub.3                                                                          H   H  H C.sub.2 H.sub.5                                                                   OCH.sub.3                                                                            ##STR292##                                                                           CH.sub.3                                 271   CH.sub.3                                                                          H   H  H C.sub.2 H.sub.5                                                                   OCH.sub.3                                                                            ##STR293##                                                                           OCH.sub.3                                272   OCH.sub.3                                                                         H   CH.sub.3                                                                         H CH.sub.3                                                                          H                                                                                    ##STR294##                                                                           CH.sub.3                                 273   OCH.sub.3                                                                         H   CH.sub.3                                                                         H CH.sub.3                                                                          H                                                                                    ##STR295##                                                                           OCH.sub.3                                274   H   H   CH.sub.3                                                                         H CH.sub.3                                                                          CH.sub.3                                                                             ##STR296##                                                                           H                                        275   H   H   CH.sub.3                                                                         H CH.sub.3                                                                          CH.sub.3                                                                             ##STR297##                                                                           CH.sub.3                                 276   H   H   CH.sub.3                                                                         H CH.sub.3                                                                          CH.sub.3                                                                             ##STR298##                                                                           OCH.sub.3                                277   H   H   CH.sub.3                                                                         H CH.sub.3                                                                          OCH.sub.3                                                                            ##STR299##                                                                           H                                        278   H   H   CH.sub.3                                                                         H CH.sub.3                                                                          OCH.sub.3                                                                            ##STR300##                                                                           CH.sub.3                                 279   H   H   CH.sub.3                                                                         H CH.sub.3                                                                          OCH.sub.3                                                                            ##STR301##                                                                           OCH.sub.3                                280   OCH.sub.3                                                                         H   H  H CH.sub.3                                                                          C.sub.2 H.sub.5                                                                      ##STR302##                                                                           CH.sub.3                                 281   OCH.sub.3                                                                         H   H  H CH.sub.3                                                                          C.sub.2 H.sub.5                                                                      ##STR303##                                                                           OCH.sub.3                                282   OCH.sub.3                                                                         H   H  H CH.sub.3                                                                          .sup.i C.sub.3 H.sub.7                                                               ##STR304##                                                                           CH.sub.3                                 283   OCH.sub.3                                                                         H   H  H CH.sub.3                                                                          .sup.i C.sub.3 H.sub.7                                                               ##STR305##                                                                           OCH.sub.3                                284   OCH.sub.3                                                                         H   H  H C.sub.2 H.sub.5                                                                   C.sub.2 H.sub.5                                                                      ##STR306##                                                                           CH.sub.3                                 285   OCH.sub.3                                                                         H   H  H C.sub.2 H.sub.5                                                                   C.sub.2 H.sub.5                                                                      ##STR307##                                                                           OCH.sub.3                                286   OCH.sub.3                                                                         H   H  H C.sub.2 H.sub.5                                                                   .sup.n C.sub.3 H.sub.7                                                               ##STR308##                                                                           H                                        287   OCH.sub.3                                                                         H   H  H C.sub.2 H.sub.5                                                                   .sup.n C.sub.3 H.sub.7                                                               ##STR309##                                                                           CH.sub.3                                 288   OCH.sub.3                                                                         H   H  H C.sub.2 H.sub.5                                                                   .sup.n C.sub.3 H.sub.7                                                               ##STR310##                                                                           OCH.sub.3                                289   O(CH.sub.2).sub.2 O                                                                   H  H CH.sub.3                                                                          H                                                                                    ##STR311##                                                                           CH.sub.3                                 290   O(CH.sub.2).sub.2 O                                                                   H  H C.sub.2 H.sub.5                                                                   H                                                                                    ##STR312##                                                                           CH.sub.3                                 291   O(CH.sub.2).sub.2 O                                                                   H  H C.sub.2 H.sub.5                                                                   H                                                                                    ##STR313##                                                                           OCH.sub.3                                292   O(CH.sub.2).sub.2 O                                                                   H  H .sup.i C.sub.3 H.sub.7                                                            H                                                                                    ##STR314##                                                                           H                                        293   O(CH.sub.2).sub.2 O                                                                   H  H .sup.i C.sub.3 H.sub.7                                                            H                                                                                    ##STR315##                                                                           CH.sub.3                                 294   O(CH.sub.2).sub.2 O                                                                   H  H .sup.i C.sub.3 H.sub.7                                                            H                                                                                    ##STR316##                                                                           OCH.sub.3                                295   O(CH.sub.2).sub.2 O                                                                   CH.sub.3                                                                         H CH.sub.3                                                                          H                                                                                    ##STR317##                                                                           CH.sub.3                                 296   O(CH.sub.2).sub.2 O                                                                   CH.sub.3                                                                         H CH.sub.3                                                                          H                                                                                    ##STR318##                                                                           OCH.sub.3                                297   O(CH.sub.2).sub.2 O                                                                   H  H CH.sub.3                                                                          CH.sub.3                                                                             ##STR319##                                                                           CH.sub.3                                 298   O(CH.sub.2).sub.2 O                                                                   H  H CH.sub.3                                                                          CH.sub.3                                                                             ##STR320##                                                                           OCH.sub.3                                299   O(CH.sub.2).sub.2 O                                                                   H  H CH.sub.3                                                                          C.sub.2 H.sub.5                                                                      ##STR321##                                                                           H                                        300   O(CH.sub.2).sub.2 O                                                                   H  H CH.sub.3                                                                          C.sub.2 H.sub.5                                                                      ##STR322##                                                                           CH.sub.3                                 301   O(CH.sub.2).sub.2 O                                                                   H  H CH.sub.3                                                                          C.sub.2 H.sub.5                                                                      ##STR323##                                                                           OCH.sub.3                                302   O(CH.sub.2).sub.2 O                                                                   H  H CH.sub.3                                                                          .sup.i C.sub.3 H.sub.7                                                               ##STR324##                                                                           CH.sub. 3                                303   O(CH.sub.2).sub.2 O                                                                   H  H CH.sub.3                                                                          .sup.i C.sub.3 H.sub.7                                                               ##STR325##                                                                           OCH.sub.3                                304   O(CH.sub.2).sub.2 O                                                                   H  H C.sub.2 H.sub.5                                                                   C.sub.2 H.sub.5                                                                      ##STR326##                                                                           CH.sub.3                                 305   O(CH.sub.2).sub.2 O                                                                   H  H C.sub.2 H.sub.5                                                                   C.sub.2 H.sub.5                                                                      ##STR327##                                                                           OCH.sub.3                                306   O(CH.sub.2).sub.2 O                                                                   H  H C.sub.2 H.sub.5                                                                   .sup.n C.sub.3 H.sub.7                                                               ##STR328##                                                                           H                                        307   O(CH.sub.2).sub.2 O                                                                   H  H C.sub.2 H.sub.5                                                                   .sup.n C.sub.3 H.sub.7                                                               ##STR329##                                                                           CH.sub.3                                 308   O(CH.sub.2).sub.2 O                                                                   H  H C.sub.2 H.sub.5                                                                   .sup.n C.sub.3 H.sub.7                                                               ##STR330##                                                                           OCH.sub.3                                309   CH.sub.3                                                                          CH.sub.3                                                                          H  CCl.sub.2                                                                           CH.sub.3                                                                             ##STR331##                                                                           CH.sub.3                                 310   CH.sub.3                                                                          CH.sub.3                                                                          H  CCl.sub.2                                                                           CH.sub.3                                                                             ##STR332##                                                                           OCH.sub.3                                311                                                                                  ##STR333##                                                                                           ##STR334##                                                                           H                                        312                                                                                  ##STR335##                                                                                           ##STR336##                                                                           CH.sub.3                                 313                                                                                  ##STR337##                                                                                           ##STR338##                                                                           OCH.sub.3                                314                                                                                  ##STR339##                                                                                           ##STR340##                                                                           H                                        315                                                                                  ##STR341##                                                                                           ##STR342##                                                                           CH.sub.3                                 316                                                                                  ##STR343##                                                                                           ##STR344##                                                                           OCH.sub.3                                317   CH.sub.3                                                                          CH.sub.3                                                                          H  H CH.sub.3                                                                          OH                                                                                   ##STR345##                                                                           H                                        318   CH.sub.3                                                                          CH.sub.3                                                                          H  H CH.sub.3                                                                          OH                                                                                   ##STR346##                                                                           CH.sub.3                                 319   CH.sub.3                                                                          CH.sub.3                                                                          H  H CH.sub.3                                                                          OH                                                                                   ##STR347##                                                                           OCH.sub.3                                __________________________________________________________________________

                  TABLE 5                                                         ______________________________________                                         ##STR348##                                                                    No.Compound                                                                           R.sup.17                                                                             R.sup.18                                                                              R.sup.19                                                                           R.sup.20                                                                           ##STR349##                                                                              B                                 ______________________________________                                        320     CH.sub.3                                                                             H       H    H                                                                                   ##STR350##                                                                             CH.sub.3                           321     CH.sub.3                                                                             H       H    H                                                                                   ##STR351##                                                                             OCH.sub.3                          322     CH.sub.3                                                                             H       H    H                                                                                   ##STR352##                                                                             H                                  323     CH.sub.3                                                                             H       H    H                                                                                   ##STR353##                                                                             CH.sub.3                           324     CH.sub.3                                                                             H       H    H                                                                                   ##STR354##                                                                             OCH.sub.3                          325     CH.sub.3                                                                             CH.sub.3                                                                              H    H                                                                                   ##STR355##                                                                             CH.sub.3                           326     CH.sub.3                                                                             CH.sub.3                                                                              H    H                                                                                   ##STR356##                                                                             OCH.sub.3                          327     CH.sub.3                                                                             CH.sub.3                                                                              H    H                                                                                   ##STR357##                                                                             CH.sub.3                           328     CH.sub.3                                                                             CH.sub.3                                                                              H    H                                                                                   ##STR358##                                                                             OCH.sub.3                          329     H      H       CH.sub.3                                                                           CH.sub.3                                                                            ##STR359##                                                                             CH.sub.3                           330     H      H       CH.sub.3                                                                           CH.sub.3                                                                            ##STR360##                                                                             OCH.sub.3                          331     CH.sub.3                                                                             OCH.sub.3                                                                             H    H                                                                                   ##STR361##                                                                             H                                  332     CH.sub.3                                                                             OCH.sub.3                                                                             H    H                                                                                   ##STR362##                                                                             CH.sub.3                           333     CH.sub.3                                                                             OCH.sub.3                                                                             H    H                                                                                   ##STR363##                                                                             OCH.sub.3                          ______________________________________                                    

                  TABLE 6                                                         ______________________________________                                         ##STR364##                                                                    Compound No.                                                                             R.sup.21                                                                              R.sup.22                                                                              ##STR365##                                                                              B                                       ______________________________________                                        334        .sup.i C.sub.3 H.sub.7                                                                H                                                                                      ##STR366##                                                                             H                                        335        .sup.i C.sub.3 H.sub.7                                                                H                                                                                      ##STR367##                                                                             CH.sub.3                                 336        .sup.i C.sub.3 H.sub.7                                                                H                                                                                      ##STR368##                                                                             OCH.sub.3                                337        .sup.i C.sub.4 H.sub.9                                                                H                                                                                      ##STR369##                                                                             CH.sub.3                                 338        .sup.i C.sub.4 H.sub.9                                                                H                                                                                      ##STR370##                                                                             OCH.sub.3                                339        H       C.sub.2 H.sub.5                                                                        ##STR371##                                                                             CH.sub.3                                 340        H       C.sub.2 H.sub.5                                                                        ##STR372##                                                                             OCH.sub.3                                341        H       .sup.n C.sub.3 H.sub.7                                                                 ##STR373##                                                                             H                                        342        H       .sup.n C.sub.3 H.sub.7                                                                 ##STR374##                                                                             CH.sub.3                                 343        H       .sup.n C.sub.3 H.sub.7                                                                 ##STR375##                                                                             OCH.sub.3                                344        H       .sup.i C.sub.3 H.sub.7                                                                 ##STR376##                                                                             CH.sub.3                                 345        H       .sup.i C.sub.3 H.sub.7                                                                 ##STR377##                                                                             OCH.sub.3                                ______________________________________                                    

                  TABLE 7                                                         ______________________________________                                         ##STR378##                                                                    pound No.Com-                                                                          R.sup.23                                                                             R.sup.24                                                                             R.sup.25                                                                           R.sup.26                                                                           ##STR379##                                                                              B                                 ______________________________________                                        346      H      H      CH.sub.3                                                                           H                                                                                   ##STR380##                                                                             CH.sub.3                           347      H      H      CH.sub.3                                                                           H                                                                                   ##STR381##                                                                             OCH.sub.3                          348      H      H      CH.sub.3                                                                           H                                                                                   ##STR382##                                  349      H      H      CH.sub.3            CH.sub.3                                                       H                                                                                   ##STR383##                                                                             OCH.sub.3                          350      H      H      CH.sub.3                                                                           CH.sub.3                                                                            ##STR384##                                                                             H                                  351      H      H      CH.sub.3                                                                           CH.sub.3                                                                            ##STR385##                                                                             CH.sub.3                           352      H      H      CH.sub.3                                                                           CH.sub.3                                                                            ##STR386##                                                                             OCH.sub.3                          ______________________________________                                    

                  TABLE 8                                                         ______________________________________                                         ##STR387##                                                                    Compound No.                                                                            R.sup.27                                                                             R.sup.28                                                                              R.sup.29                                                                            ##STR388##                                                                              B                                   ______________________________________                                        353       H      CH.sup.3                                                                              CH.sup.3                                                                             ##STR389##                                                                             CH.sup.3                             354       H      CH.sup.3                                                                              CH.sup.3                                                                             ##STR390##                                                                             OCH.sup.3                            ______________________________________                                    

                  TABLE 9                                                         ______________________________________                                         ##STR391##                                                                    Compound No.                                                                            R.sup.30                                                                              R.sup.31                                                                                ##STR392##                                                                              B                                      ______________________________________                                        355       CH.sub.3                                                                              CH.sub.3                                                                                 ##STR393##                                                                             H                                       356       CH.sub.3                                                                              CH.sub.3                                                                                 ##STR394##                                                                             CH.sub.3                                357       CH.sub.3                                                                              CH.sub.3                                                                                 ##STR395##                                                                             OCH.sub.3                               ______________________________________                                    

                  TABLE 10                                                        ______________________________________                                         ##STR396##                                                                    Compound No.                                                                            R.sup.32                                                                             R.sup.33                                                                              R.sup.34                                                                            ##STR397##                                                                              B                                   ______________________________________                                        358       CH.sub.3                                                                             CH.sub.3                                                                              CH.sub.3                                                                             ##STR398##                                                                             H                                    359       CH.sub.3                                                                             CH.sub.3                                                                              CH.sub.3                                                                             ##STR399##                                                                             CH.sub.3                             360       CH.sub.3                                                                             CH.sub.3                                                                              CH.sub.3                                                                             ##STR400##                                                                             OCH.sub.3                            361       CH.sub.3                                                                             CH.sub.3                                                                              C.sub.2 H.sub.5                                                                      ##STR401##                                                                             H                                    362       CH.sub.3                                                                             CH.sub.3                                                                              C.sub.2 H.sub.5                                                                      ##STR402##                                                                             CH.sub.3                             363       CH.sub.3                                                                             CH.sub.3                                                                              C.sub.2 H.sub. 5                                                                     ##STR403##                                                                             OCH.sub.3                            ______________________________________                                    

                  TABLE 11                                                        ______________________________________                                         ##STR404##                                                                    pound No.Com-                                                                         R.sup.35                                                                             R.sup.36                                                                             R.sup.37                                                                            R.sup.38                                                                           ##STR405##                                                                              B                                 ______________________________________                                        364     H      H      CH.sub.3                                                                            CH.sub.3                                                                            ##STR406##                                                                             CH.sub.3                           365     H      H      CH.sub.3                                                                            CH.sub.3                                                                            ##STR407##                                                                             OCH.sub.3                          366     H      H      OCH.sub.3                                                                           CH.sub.3                                                                            ##STR408##                                                                             H                                  367     H      H      OCH.sub.3                                                                           CH.sub.3                                                                            ##STR409##                                                                             CH.sub.3                           368     H      H      OCH.sub.3                                                                           CH.sub.3                                                                            ##STR410##                                                                             OCH.sub.3                          369     H      CH.sub.3                                                                             OCH.sub.3                                                                           CH.sub.3                                                                            ##STR411##                                                                             H                                  370     H      CH.sub.3                                                                             OCH.sub.3                                                                           CH.sub.3                                                                            ##STR412##                                                                             CH.sub.3                           371     H      CH.sub.3                                                                             OCH.sub.3                                                                           CH.sub.3                                                                            ##STR413##                                                                             OCH.sub.3                          ______________________________________                                    

The compound of formula (I) provided by this invention can be produced,for example, by reacting an aminopyridine or an aniline derivativerepresented by the following formula (II) ##STR414## wherein Ar and Aare as defined with regard to formula [I], with methyl isocyanate,N,N-dimethylcarbamoyl chloride or N-methoxy-N-methylcarbamoyl chloride.

The compound of formula [II] used in the above reaction can be producedby a synthesis route consisting of the following reactions (1) and (2).##STR415##

In performing the reaction (1), known reaction means of forming anaromatic ether compound by reaction of a phenolic hydroxyl group with anaryl chloride may be applied. Specifically, it can be carried out bystirring the reaction mixture at a temperature of 20° to 150° C., for0.5 to 10 hours in an aromatic hydrocarbon (e.g., benzene, toluene,xylene), in an aprotic polar solvent (e.g., N,N-dimethylformamide,1-methyl-2-pyrrolidone) or in their mixture in the presence of a basesuch as sodium hydroxide, potassium hydroxide, sodium carbonate andpotassium carbonate. After the reaction, the compound [V] can beisolated by a known means such as column chromatography.

On the other hand, known means of producing an aromatic amine byreducing an aromatic nitro compound with hydrogen may be applied to thepractice of the reaction (2). Specifically, the reduction with hydrogencan be carried out at a temperature of 20° to 200° C. under normalpressure to 20 kg/cm² of hydrogen in an inert solvent such as benzene,toluene, xylene, methanol, ethanol or ethyl acetate in the presence ofan ordinary reducing catalyst such as Raney nickel or palladium-carbon.After the reaction, the compound [II] can be isolated by operationsincluding removal of the catalyst, removal of the solvent, and asrequired, recrystallization.

Referential Examples 39 and 41 given hereinbelow illustrate thesynthesis of compound [V] by the reaction (1). Synthesis of compound[II] by the reaction (2) is illustrated in Referential Examples 40, 42,45, 47 and 48 given hereinbelow.

Among the compounds of general formula [V], compounds of the followinggeneral formula [V-1] ##STR416## in which R¹⁶ is a lower alkoxy group ora hydroxyl group, can also be produced by a synthesis route consistingof the following reactions (3) and (4). ##STR417##

After the reaction (3), the compound [VI] can be isolated by the sameoperations as in the case of obtaining the compound [V] by the abovereaction (1).

The reaction (4) proceeds by heating the reaction mixture at 40° to 120°C. in the absence of solvent or in an inert solvent such as acetone,dioxane, benzene or toluene in the presence of an acid catalyst such ashydrochloric acid, sulfuric acid and Amberlyst-15®. After the reaction,the compound [V-1] can be isolated by recrystallization, columnchromatography, etc. after optionally removing the catalyst and thesolvent.

Synthesis of the compound [VI] by the reaction (3) is shown inReferential Example 43, and synthesis of the compound [V-1] by thereaction (4), in Referential Examples 44 and 46.

Among the compounds of general formula [V], compounds of general formula[V-2] ##STR418## may also be synthesized from the compound [VI] inaccordance with the following reaction (5). ##STR419##

Known procedures of reacting a cyclohexene ring with dichlorocarbene tointroduce a dichloromethylene group into the double bond portion of thecyclohexene ring may be applied to the practice of the reaction (5).Specifically, the reaction (5) proceeds by stirring the compound [VI],chloroform and sodium or potassium hydroxide in the absence of solventor in water as a solvent in the presence of a quaternary ammonium saltsuch as benzyltrimethylammonium chloride.

Referential Example 48 illustrates the production of a compound ofgeneral formula [V-2] by the reaction (5).

Use of a base in the reaction of the compound of formula [II] with thecarbamoyl chloride can increase the yield of the product. Examples ofthe base are pyridines such as pyridine, picoline, lutidine, andcollidine, tertiary amines such as triethylamine,1,8-diazabicyclo[5,4,0]undecene-7 and N,N-dimethylaniline, and inorganicbases such as sodium bicarbonate, potassium bicarbonate, sodiumcarbonate, potassium carbonate, sodium hydroxide and potassiumhydroxide. The amount of the base used is from 0.5 to 20, preferablyfrom 1 to 10, as the molar ratio to the carbamoyl chloride.

The reaction of the compound [II] with methyl isocyanate proceeds in theabsence of a catalyst, but as required, may be carried out in thepresence of 0.1 to 5 mole%, based on the compound [II], of a tertiaryamine such as triethylamine.

The use of a reaction solvent is not necessary, but there may be used asolvent inert to the reaction, for example an aromatic hydrocarbon suchas benzene, toluene and xylene, a halogenated hydrocarbon such aschloroform, dichloromethane, carbon tetrachloride, dichloroethane,trichloroethane, tetrachloroethane, chlorobenzene or dichlorobenzene,tetrahydrofuran, ethyl acetate or dimethylformamide, either alone or incombination.

The reaction is carried out by mixing 1 mole of the aminopyridinederivative or aniline derivative [II] and 0.8 to 3 moles, preferably 1to 2 moles, of methyl isocyanate or the carbamoyl chloride with orwithout the base in the absence of solvent or in the aforesaid solvent,and stirring the mixture at a temperature of -20° to 100° C., preferably0° to 80° C., for 0.3 to 30 hours.

After the reaction, the final desired product can be obtained by variousseparation methods shown in Examples given hereinbelow.

According to another embodiment of producing the compound of formula[I], the compound of formula [I] can be produced by reacting anisocyanate derivative represented by the following formula [III]##STR420## wherein Ar and A are as defined with regard to formula [I],with an amine compound represented by the following formula [IV]##STR421## wherein B is as defined with regard to formula [I].

The isocyanate derivative [III] may be obtained by subjecting thecompound [II] to a known means of reacting an aniline with phosgene tosynthesize a phenyl isocyanate. Referential Example 49 given hereinbelowillustrate synthesis of one example of the compound of formula [III].

Known means of reacting an isocyanate ester with an amine to form a ureamay be applied to the practice of the reaction of the isocyanatederivative [III] with the amine [IV]. The reaction may be carried outwithout a reaction solvent. If desired, however, there may be used asolvent inert to the reaction, for example an aromatic hydrocarbon suchas benzene, toluene or xylene, a halogenated hydrocarbon such aschloroform, dichloromethane, carbon tetrachloride, dichloroethane,trichloroethane, tetrachloroethane, chlorobenzene or dichlorobenzene,tetrahydrofuran, dioxane, ethyl acetate and dimethylformamide.

The reaction is carried out by mixing 1 mole of the isocyanatederivative and 0.8 to 5 moles, preferably 1 to 2 moles, of the amine inthe absence of a solvent or in the aforesaid solvent, and stirring themixture at a temperature of -20° to 100° C., preferably 0° to 50° C.,for 0.5 to 30 hours.

After the reaction, the desired product may be isolated by aconventional procedure such as the one shown in Example 3 givenhereinbelow.

Guidelines for the synthesis of the compounds of the general formulaAr-OH used in the synthesis of the compounds [V] by the reaction (1) areshown in the reaction schemes given in the column of Synthesis Method inTable 12. Precursor Nos. 1 to 38 in Table 12 correspond respectively toReferential Examples 1 to 38 given hereinbelow. For example, theprecursor for which a synthesis method is described in ReferentialExample 1 is one example of compounds which belong to the precursor No.1.

Table 12 also describes literature references which are closely relatedto the reaction schemes of the synthesis methods.

It is believed that one skilled in the art can easily understand themethod of synthesis of Ar-OH when he refers to Table 12 and ReferentialExamples 1 to 38.

Japanese patent application No. 279,193/1985 cited as reference for theprecursor No. 2 was filed on the basis of an invention made by two ofthe inventors of the present application and has not yet been published.Precursor No. 2 may be synthesized in accordance with this method byreacting 1 mole of 1,3-dihydroxybenzene and about 0.5 to 5 moles of aketone in the presence or absence of a solvent using an acid catalystsuch as hydrochloric acid, sulfuric acid or a cation exchange resin atroom temperature to 120° C. for 2 to 30 hours.

In the reaction scheme for precursor No. 5, the aforesaid reactiontechnique can be applied to the first reaction, and the subsequenthydrogenation reaction is well known per se.

There has been no prior example in which the precursor No. 24 shown inTable 12 was synthesized by the synthesis route shown in the reactionscheme in Table 12. In the reaction scheme, the reaction of a ketonewith ethylene glycol to form a 5-membered ring comprising anethylenedioxy group is well known per se, and the reaction of formingthe phenolic hydroxyl group by the reaction of hydrogen on phenylbenzylether is also well known. Hence, the precursor 24 can be easilysynthesized by following this reaction scheme and Referential Example24.

The reaction for producing precursor No. 26 is neither known heretofore,and was discovered for the first time by the inventors of the presentapplication. This reaction proceeds by reacting the two reactants underice cooling in the presence of an alcohol of the formula R₁₅ --H usingan acid catalyst such as sulfuric acid, toluenesulfonic acid or a cationexchange resin.

In Table 12, Bz in Table 12 stands for the benzyl group.

The method of synthesizing the starting material of the followingformula ##STR422## used in the reaction (3) above is described, forexample, in U.S. Pat. No. 4,323,505.

Referential Examples 1 to 38 given hereinbelow illustrate synthesis oftypical compounds of general formula Ar--OH.

Referential Examples 39 and 41 show synthesis of intermediates comingwithin the scope of compounds [V] in accordance with the reaction (1).Referential Examples 40, 42, 45 and 47 show synthesis of intermediatescoming within the scope of compounds [II] in accordance with thereaction (2). Referential Example 43 shows synthesis of an intermediatecoming within the scope of compounds [VI] in accordance with thereaction (3). Referential Example 48 shows synthesis of an intermediatefalling within the scope of compound [V-2] in accordance with thereaction 5 and subsequent synthesis of an intermediate coming within thescope of compound [II] by the reaction 2. Referential Example 49 showssynthesis of an intermediate falling within the scope of compound [III].

In these Referential Examples, column chromatography was carried outusing a silica gel column and hexane-ethyl acetate mixture as an eluent.

    TABLE 12      Precursor    No. ArOH Synthesis method Reference           1      ##STR423##      ##STR424##      J. C. S., 2254(1948)      ##STR425##      2     ##STR426##      ##STR427##      Japanese Pat. Appln.No. 279193/1985      3     ##STR428##      ##STR429##      J. Am. Chem. Soc.,70, 3619 (1948)      ##STR430##      4     ##STR431##      ##STR432##      Aust. J. Chem.,22, 601 (1969)      ##STR433##      5     ##STR434##      ##STR435##      Japanese Pat. Appln.No. 279193/1985      ##STR436##      6     ##STR437##      ##STR438##      J. Org. Chem.,35, 2904 (1970)      7     ##STR439##      ##STR440##      J. Org. Chem.,28, 2469 (1963)      ##STR441##      Indian J. Chem.,7, 1004 (1969)      8     ##STR442##      ##STR443##      Japanese Laid-OpenPat. Publn.No. 149263/1976      ##STR444##      9     ##STR445##      ##STR446##      Japanese Laid-OpenPat. Publn.No. 149263/1976      10     ##STR447##      ##STR448##      J. Org. Chem.,29, 2579 (1964)      11     ##STR449##      ##STR450##      J. Org. Chem.,29, 2579 (1964)      ##STR451##      12     ##STR452##      ##STR453##      J. Org. Chem.,29, 2579 (1964)      ##STR454##      13     ##STR455##      ##STR456##      J. Org. Chem.,29, 2579 (1964)      ##STR457##      17     ##STR458##      ##STR459##      J. Org. Chem.,26, 240 (1961);      ##STR460##      J. Am. Chem. Soc.,94, 9166 (1972)      18     ##STR461##      ##STR462##      Bull. Soc. Chim.France, 776 (1957),      ##STR463##      J. Am. Chem. Soc.,94, 9166 (1972)      14     ##STR464##      ##STR465##      Aust. J. Chem.,33, 675 (1980)  R.sup.9, R.sup.10 : alkyl,or R.sup.9 and     R.sup.10are bondedthrough analkylene chain      ##STR466##      15     ##STR467##      ##STR468##      Ger. Offen.2,550,965  R.sup.9 : alkoxy  R.sup.10 : H, alkyl   16      ##STR469##      ##STR470##      J. Am. Chem. Soc.,94, 9166 (1972)      ##STR471##      19     ##STR472##      ##STR473##      Journal ofJap. Chem. Soc.,1987 (1972)  R: H, CH.sub.3  R.sup.15 :     CH.sup.3  R.sup.16 : H, CH.sub.3      20     ##STR474##      ##STR475##      Japanese Laid-OpenPat. Publn.No. 5475/1981      21     ##STR476##      ##STR477##      Japanese Laid-OpenPat. Publn.No. 109779/82      22     ##STR478##      ##STR479##      Angew. Chem.Int. Ed.Engl. 21, 225(1982)  R.sup.15 : alkylR.sup.16 : H,     alkylor R.sup.15 and R.sup.16are bondedthrough analkylene chain      ##STR480##      23     ##STR481##      ##STR482##      Angew. Chem.Int. Ed.Engl. 21, 225(1982)  R.sup.11 : alkoxyR.sup.15 :     alkyl R.sup.16      : H, alkyl     ##STR483##      24     ##STR484##      ##STR485##      25     ##STR486##      ##STR487##      U.S. Pat. No.4,003,919   R: H, CH.sub.3  R.sup.11, R.sup.13, R.sup.15 :      H, alkyl  R.sup.16 : alkoxy or  R.sup.11 and R.sup.15 are  bonded     through  an alkylene  chain      26     ##STR488##      ##STR489##       R.sup.11 : H, alkyl  R.sup.15 : alkoxy      27     ##STR490##      ##STR491##      Bull. Chem. Soc.Japan, 31, 397(1958)      ##STR492##      28     ##STR493##      ##STR494##      Bull, Chem. Soc.Japan, 31, 397(1958)      ##STR495##      29     ##STR496##      ##STR497##      Aust. J. Chem.,22, 601 (1969)      ##STR498##      30     ##STR499##      ##STR500##      J. Chem. Soc.,1190 (1958)      ##STR501##      31     ##STR502##      ##STR503##      Ger. Offen.1,945,212      32     ##STR504##      ##STR505##      U.S. Pat. No. 4,003,919      33     ##STR506##      ##STR507##      Bull. Soc. Chim.France, 776 (1957);J. Am. Chem. Soc.,94, 9166 (1972)      ##STR508##      34     ##STR509##      ##STR510##      J. Org. Chem.,29, 2579 (1964)      35     ##STR511##      ##STR512##      J. Org. Chem.,29, 2579 (1964)      36     ##STR513##      ##STR514##      J. Org. Chem.,28, 2468 (1963);Indian J. Chem.,7, 1004 (1969)      ##STR515##      37     ##STR516##      ##STR517##      Ger. Offen.1,945,212      38     ##STR518##      ##STR519##      Ger. Offen.2,221,706

The compounds of formula [I] provided by this invention have lowphytotoxicity to useful crops and are useful for controlling oreradicating undesired vegetation at low dosasges. Thus, according tothis invention, there can be provided a herbicidal compositioncomprising a herbicidally effective amount of at least one compound offormula [I] and an agriculturally acceptable diluent or carrier.

The herbicidal composition may be in various formulations such asemulsifiable concentrates, wettable powders, dusts, or granules.Suitable agriculturally acceptable diluents or carriers include, forexample, solid diluents or carriers such as clay, talc, bentonite,kaolin, diatomaceous earth, white carbon, vermiculite, slaked lime, andsilica sand, and liquid diluents or carriers including solvents andsurfactants, such as alkylbenzenesulfate esters, alkylbenzenesulfonatesalts, polyoxyethylene glycol ether, polyoxyethylene alkyl aryl ethers,polyoxyethylene sorbitan monoalkylates, sodium alkylsulfates, sodiumalkylnaphthalenesulfonates, and sodium ligninsulfonate.

The herbicidal composition of the invention may contain the compound offormula [I] in a herbicidally effective amount which, for example, isabout 0.5 to about 70% by weight, based on the weight of thecomposition, and is usually from 0.5 to 20% by weight for granules ordusts, and from 5 to 70% by weight for emulsifiable concentrates orwettable powders, based on the weight of the composition.

According to this invention there may also be provided a method ofcontrolling the growth of undesired vegetation which comprises applyinga herbicidally effective amount of at least one compound represented byformula [I] to the weeds or the locus of such weeds.

The compound of formula [I], either as such or as the aforesaidcomposition or as a dilution or suspension of it in water, etc., can beapplied to the locus where undesired vegetation is growing or is likelyto grow. In the method of controlling the growth of undesiredvegetation, the rate of application of the compound of formula [I] maybe varied depending upon the formulation, the crop to be applied, theweed to be applied, climatic conditions, etc. For example, it is about50 g to about 3 kg/hectare.

The herbicide of this invention exhibits a high herbicidal efficacy bysoil treatment or foliar treatment against various weeds, particularlyvarious weeds in upland farms, for example important weeds such asbarnyard grass (Echinochloa crus-galli), fingergrass (Digitariasanguinalis), dent foxtail (Alopecurus aequalis), cocklebur (Xanthiumstrumarium), blackjack (Bidens pilosa), and velvet leaf (Abutilantheophrasti) and also weeds of Compositae, Rubiaceae, Scrophulariaceae,Solanaceae, Umbelliferae, Violaceae, Oxalidaceae, Euphorbiaceae,Brassicaceae, Caryophyllaceae, Amaranthaceae, Chenopudiaceae, andPolygonaceae. Particularly, in foliar treatment, it can be used safelyon important crops, for example gramineous crops such as wheat, corn andrice and leguminous crops such as soybean and peanut, and can kill awide range of weeds at low dosages.

The herbicide of this invention may also be applied to lawns, orchards,pastures and non-agricultural lands.

As desired, the herbicide of this invention may be used as a mixturewith, or jointly with, other agricultural chemicals such as anotherherbicide, a fungicide or an insecticide, or a fertilizer. Examples ofthe other agricultural chemicals include methyl2-[4-(2,4-dichlorophenoxy)phenoxy]propionate, isobutyl2-[4-(4-chlorophenoxy)phenoxy]propionate,2-[4-(3,5-dichloro-2-pyridyloxy)phenoxy]propionic acid, butyl2-[4-(5-trifluoromethyl-2-pyridyloxy)phenoxyl]propionate, dimethyltetrachloroterephthalate, isopropyl-N-phenylcarbamate,4-chloro-2-butynyl-N-(3-chlorophenyl)carbamate, methylN-(3,4-dichlorophenyl)carbamate, S-ethyl N,N-diisobuthylthiocarbamate,S-(2,3,3-trichloro-2-propenyl) N,N-diisopropylthiocarbamate,2-chloro-N-isopropylacetanilide,2-chloro-2',6'-diethyl-N-methoxymethylacetanilide,2-chloro-N-ethoxymethyl-2'-ethyl-6'-methylacetanilide,2-chloro-2'-ethyl-N-(2-methoxy-1-methylethyl)-6'-methylacetanilide,3',4'-dichloropropionanilide, ethyl2-[N-benzoyl-N-(3,4-dichlorophenyl)amino]propionate,3-(4-chlorophenyl)-1-methoxy-1-methylurea,3-(3,4-dichlorophenyl)-1-methoxy-1-methylurea,2-(3,5-dichlorophenyl)-2-(2,2,2-trichloroethyl)oxirane,3-amino-2,5-dichlorobenzoic acid, 3,6-dichloro-2-methoxybenzoic acid,2,6-dinitro-N,N-dipropyl-4-trifluoromethylaniline,1,2-dimethyl-3,5-diphenyl-1H-pyrazolium methyl sulfate,S-2,3-dichloroallyl-N,N-diisopropyl thiolcarbamate, and ethylN-benzoyl-N-(3-chloro-4-fluorophenyl)-2-aminopropionate.

BEST MODE FOR PRACTICING THE INVENTION

The best mode of practicing the invention will be shown below byexamples of producing the synthesis intermediates of the compounds ofthis invention, examples of producing the compounds of this invention,examples of the herbicidal composition of this invention and examples ofherbicidal tests.

REFERENTIAL EXAMPLE 1 2,3-Dihydro-3-ethyl-6-hydroxybenzofuran (aprecursor of compound No. 13)

A mixture of 5.0 g of 2',4'-dihydroxypropiophenone, 5.4 g of benzylbromide, 6.2 g of potassium carbonate and 50 ml of acetone was refluxedfor 7 hours. After cooling, the solid was separated by filtration. Thefiltrate was concentrated, and the residue was separated by columnchromatography to give 4.7 g of 4'-benzyloxy-2'-hydroxypropiophenone asa white solid (yield 61%, melting point 111.5°-112.5° C.). Then, amixture of 4.5 g of this solid, 3.5 g of ethyl bromoacetate, 6.1 g ofpotassium carbonate and 45 ml of acetone was refluxed for 7.5 hours.After cooling, the solid was separated by filtration. The filtrate wasconcentrated, and the residue was purified by column chromatography togive 5.8 g of ethyl 3-benzyloxy-6-propionylphenoxyacetate as whitecrystals (yield 97%, melting point 81.5° to 82.0° C.). This ester (5.5g) was dissolved in a solution composed of 1.3 g of potassium hydroxideand 55 ml of methanol, and the solution was stirred at room temperaturefor 2 hours to hydrolyze the ester. The hydrolysis product was worked upin a customary manner to give 3.9 g (yield 77%) of3-benzyloxy-6-propionylphenoxyacetic acid as a pale yellowish orangesolid. Then, 9.3 g of sodium acetate and 39 ml of acetic anhydride wereadded to this solid, and the mixture was heated at 155° C. for 30minutes. The solvent was evaporated, and the residue was purified bycolumn chromatography to give 2.8 g (yield 95%, melting point69.5°-70.5° C.) of 6-benzyloxy-3-ethylbenzofuran as a white solid.Palladium (5%)-carbon (0.27 g) and 27 ml of acetic acid were added to2.7 g of the resulting benzofuran, and the mixture was stirred at roomtemperature for 3 hours in an atmosphere of nitrogen. The catalyst wasseparated by filtration, and the filtrate was concentrated and thenpurified by column chromatography to give 1.7 g (yield 90%) of thedesired product as a pale orange liquid.

REFERENTIAL EXAMPLE 2 2,3-Dihydro-6-hydroxy-2,2,3-trimethylbenzofuran (aprecursor of compound No. 6)

A 100 ml three-necked flask equipped with a condenser and a thermometerwas charged with 11 g (0.1 mole) of resorcinol, 8.6 g (0.1 mole) ofisopropyl methyl ketone and 1.3 g (12% by weight based on resorcinol) ofa cation exchange resin (Amberlyst-15) as a catalyst. The mixture wasstirred at 100° C. in a nitrogen atmosphere for 10 hours. After cooling,the catalyst was separated by filtration, and the residue was purifiedby column chromatography to give 11.8 g (yield 66%) of the desiredproductg as colorless needle-like crystals. Melting point: 67.5° C.

REFERENTIAL EXAMPLE 3 2,3-Dihydro-6-hydroxybenzofuran (a precurosr ofcompound No. 11)

A mixture of 18 g of resorcinol, 12 g of chloroacetonitrile, 12 g ofzinc chloride and 100 ml of diethyl ether was bubbled with HCl gas atroom temperature with stirring. The white crystals that precipitatedwere collected by filtration, and suspended in 200 ml of water. Thesuspension was refluxed for 0.5 hour. After cooling, the white crystalswere collected by filtration and refluxed together with 16 g ofpotassium acetate and 100 ml of ethanol for 0.5 hour. After cooling, 300ml of water was added and 2N-HCl was added until the solution becameacidic. As a result, 20 g of 2,3-dihydro-7-hydroxy-3-oxobenzofuran wasobtained as brown crystals. The compound was acetylated in a customarymanner. The resultig acetylated product (3.0 g) was stirred togetherwith 0.3 g of 10% palladium-carbon and 50 ml of ethanol at 60° C. for 4hours in an atmosphere of hydrogen to give 2.0 g of white crystals. Thecrystals were hydrolyzed in a customary manner to give 1.0 g (totalyield 41%) of the desired product as a brown liquid.

REFERENTIAL EXAMPLE 4 2,3-Dihydro-2-sec-butyl-6-hydroxybenzofuran (aprecursor of compound No. 29)

A mixture of 9.0 g of potassium hydroxide, 150 ml of ethanol and 10 g of2,3-dihydro-6-hydroxy-3-oxobenzofuran was stirred at room temperaturefor 0.5 hour, and then 9.7 g of ethyl methyl ketone was added. Themixture was stirred at room temperature for 16 hours. 2N-HCl was addeduntil the aqueous layer became acidic. The mixture was then extractedwith ethyl acetate. The extract was dried over magnesium sulfate, andethyl acetate was evaporated. The resulting crude crystals wererecrystallized from hexane-ethyl acetate to give 7.4 g of browncrystals. Sodium borohydride (4.0 g) was gradually added to a mixture of2.3 g of these crystals, 1.5 g of sodium hydroxide and 100 ml of water,and then the mixture was stirred at 100° C. for 2 hours. The mixture wasacidified with 2N-HCl and extracted with ethyl acetate. Afterevaporating ethyl acetate, 0.1 g of 10% palladium-carbon and 30 ml ofethanol were added to the residue, and the mixture was stirred at roomtemperature for 3 hours in an atmosphere of hydrogen. Thepalladium-carbon was separated by filtration, and the filtrate wasconcentrated. The residue was purified by column chromatography to give2.0 g (yield 36%) of the desired product as a colorless liquid.

REFERENTIAL EXAMPLE 5 2,3-Dihydro-2,3-dimethyl-6-hydroxybenzofuran (aprecursor of compound No. 17)

A mixture of 1.9 g of resorcinol, 1.8 g of 3-methoxy-2-butanone, 0.2 gof Amberlyst-15 and 2 ml of toluene was stirred at 90° C. for 10 hours.After cooling, the catalyst was separated, and the filtrate wasconcentrated. The residue was purified by column chromatography to give1.7 g of 2,3-dimethyl-6-hydroxybenzofuran as pale yellow crystals. Thecrystals were dissolved in 20 ml of acetic acid, and 0.2 g of 5%palladium-carbon was added. The mixture was stirred at room temperaturefor 12 hours in an atmosphere of hydrogen. The crude product waspurified by column chromatography to give 1.5 g (yield 54%) of thedesired product as a brown liquid.

REFERENTAIL EXAMPLE 6 2,3-Dihydro-2,2-dimethyl-6-hydroxybenzofuran (aprecursor of compound No. 32)

3-Benzyloxyphenol (5.0 g), 2.0 g of isobutyraldehyde, 0.1 g ofmethanesulfonic acid and 50 ml of toluene were put into a flask equippedwith the Dean-Stark condenser, and stirred under reflux for 4 hours.Low-boiling compounds were evaporated under reduced pressure. Theresidue was purified by column chromatography to give 3.8 g of6-benzyloxy-2,3-dihydro-2,2-dimethylbenzofuran as a brown liquid. Thisproduct was dissolved in ethanol, and 0.4 g of 5% palladium-carbon wasadded. The mixture was stirred at room temperature for 8 hours in anatmosphere of hydrogen. The catalyst was separated by filtration, andthe filtrate was concentrated. The residue was purified by columnchromatography to give 2.0 g (yield 50%) of the desired product as apale yellow liquid.

REFERENTIAL EXAMPLE 7 2,3-Dihydro-5-hydroxy-2-methylbenzofuran (aprecursor of compound No. 60)

A mixture of 4.6 g of hydroquinone, 7.5 g of hydroquinone diacetate,13.8 g of potassium carbonate, 12.1 g of allyl bromide and 60 ml ofacetone was refluxed for 4 hours. After cooling, the solid was separatedby filtration, and the filtrate was concentrated. The residue waspurified by column chromatography to give 13.6 g (yield 85%) of4-acetoxyphenyl allyl ether as a pale orange liquid. Then, 4.0 g of thisliquid was dissolved in N,N-dimethylaniline, and the solution was heatedat 210° C. for 6 hours. The crude product was purified by columnchromatography to give 3.5 g (yield 88%) of 4-acetoxy-2-allylphenol.This phenol was dissolved in a methanol solution of potassium hydroxideand hydrolyzed. The hydrolyzed product was worked up in a customarymanner, and purified by column chromatography to give 2.2 g (yield 82%)of 2-allylhydroquinone as a pale orange solid. To 1.7 g of this solidwere added 8.5 ml of acetic acid and 3.4 ml of 47% hydrobromic acid, andthe mixture was heated at 75° C. for 16 hours. The reaction mixture wasneutralized with aqueous sodium carbonate and extracted with ethylacetate. The extract was dried over magnesium sulfate, and concentrated.The residue was purified by column chromatography to give 1.4 g (yield82%) of the desired product as a reddish brown liquid.

REFERENTIAL EXAMPLE 8 2,3-Dihydro-3,3-dimethyl-5-hydroxybenzofuran (aprecursor of compound No. 88)

A solution composed of 46 ml of isobutyraldehyde and 1 ml oftriethylamine was refluxed, and a mixture of 5.0 g of p-quinone and 46ml of isobutyraldehyde was added. The mixture was refluxed for 15minutes. Low-boiling compounds were evaporated under reduced pressure.The residue was purified by column chromatography to give2-(1-formyl-1-methylethyl)hydroquinone as a deep orange liquid. Thisliquid was reduced with 0.87 g of sodium borohydride in 83 ml ofethanol, and then refluxed for 1.5 hours in 85 ml of toluene togetherwith a catalytic amount of p-toluenesulfonic acid. The crude product waspurified by column chromatography to give 4.8 g of the desired producthaving a reddish orange color.

REFERENTIAL EXAMPLE 92,3-Dihydro-3,3-dimethyl-5-hydroxy-2-methoxybenzofuran (a precursor ofcompound No. 95)

A mixture of 46 ml of isobutyraldehyde and 1.0 ml of triethylamine wasrefluxed, and a mixture of 5.0 g of p-quinone and 46 ml ofisobutyraldehyde was gradually added dropwise to the mixture. Thereaction mixture was distilled under reduced pressure, and the residuewas refluxed for 1.5 hours together with 50 ml of methanol and 0.5 g ofp-toluenesulfonic acid. The reaction mixture was extracted with ethylcetate. The extract was concentrated, and the residue was purified bycolumn chromatography to give 7.0 g (yield 79%) of the desired productas a brown liquid.

REFERENTIAL EXAMPLE 10 2,3-Dihydro-2-ethoxy-3-ethyl-5-hydroxybenzofuran(a precursor of compound No. 107)

To a solution of 20 g of p-quinone in 200 ml of toluene was added 39 gof 1-morpholino-1-butene at room temperature, and the mixture wasstirred for 6 hours. Toluene was evaporated, and the residue wasdissolved in ethanol. The solution was added dropwise to 150 ml of4N-HCl, and the mixture was stirred at room temperature, and extractedwith ethyl acetate. The extract was concentrated, and the residue waspurified by column chromatography to give 18.6 g (yield 48%) of thedesired product as a brown liquid.

REFERENTIAL EXAMPLE 11 2,3-Dihydro-3-ethyl-5-hydroxybenzofuran (aprecursor of compound No. 65)

The adduct of p-quinone and enamine shown in Referential Example 10 (5.0g) was stirred together with 150 ml of 4N-HCl at room temperature for 16hours. The crude product was purified by column chromatography to give1.6 g (yield 49%) of 3-ethyl-5-hydroxybenzofuran. This product washydrogenated in isopropanol at room temperature for 7 hours in thepresence of a catalytic amount of Raney nickel to give 1.6 g (yield 99%)of the desired product as a brown liquid.

REFERENTIAL EXAMPLE 12 2,3-Dihydro-5-hydroxy-2-sec-butylbenzofuran (aprecursor of compound No. 73)

Referential Example 11 was repeated except that4-methyl-2-morpholino-1-pentene was used as the enamine. The desiredcompound was obtained as a brown liquid in a yield of 41%.

REFERENTIAL EXAMPALE 13 1,2,3,4,4a,9b-hexahydro-8-hydroxydibenzofuran (aprecursor of compound No. 117)

Referential Example 11 was repeated except that1-morpholino-1-cyclohexene was used as the enamine. The desired compoundwas obtained as a brown liquid in a yield of 63%.

REFERENTIAL EXAMPLE 14 2-Ethyl-5-hydroxy-2-methyl-1,3-dioxolane (aprecursor of compound No. 129)

Catechol (20 g), 55 ml of methyl ethyl ketone, 10 mg ofp-toluenesulfonic acid and 100 ml of toluene were put into a flaskequipped with the Dean-Stark condenser, and refluxed for 36 hours togive 23.6 of 2-ethyl-2-methyl-1,3-dioxolane as a colorless liquid. Theliquid was stirred in acetic acid together with 127 g of Pb(OAc)₄ at140° C. for 9.5 hours. The crude product was purified by columnchromatography to give 7.2 g of the acetoxylated product as a brownliquid. This liquid was hydrolyzed using potassium hydroxide, methanoland water to give 5.8 g (yield 18%) of the desired product as a brownliquid.

REFERENTIAL EXAMPLE 15 2-Ethoxy-5-hydroxy-2-methyl-1,3-dioxolane (aprecursor of compound No. 138)

A solution composed of 5.0 g of 1,2,4-trihydroxybenzene, 9.7 g oftriethyl orthoacetate and 50 ml of toluene-carbon tetrachloride (1:1)was refluxed for 1.5 hours. The solvent was evaporated, and the residuewas purified by column chromatography to give 6.7 g (yield 86%) of thedesired product as pale brown crystals having a melting point of 86° to87° C.

REFERENTIAL EXAMPLE 16 2,3-Dihydro-7-hydroxy-4H-1-benzopyran (aprecursor of compound No. 155)

5.0 g of 7-hydroxycoumarin was hydrogenated using 0.5 g of 5%palladium-carbon as a catalyst at 80° C. for 9 hours in 13 ml of aceticacid and 25 ml of ethyl acetate. The reaction residue was recrystallizedfrom hexane-ethyl acetate to give 4.9 g of white crystals (m.p.135°-137° C.). The crystals were dissolved in 15 ml of tetrahydrofuran,and the solution was added dropwise at room temperature to a mixture of0.9 g of lithium aluminum hydride and 10 ml of tetrahydrofuran, and themixture was then refluxed for 3 hours. The reaction mixture was workedup in a customary manner, and the product was dissolved in 30 ml oftoluene without purification. A catalytic amount of p-toluenesulfonicacid was added, and the mixture was heated at 120° C. for 6 hours. Thereaction mixture was worked up in a customary manner. The residue afterconcentration was purified by column chromatography to give 1.6 g (yield36%) of the desired product as pink crystals.

REFERENTIAL EXAMPLE 172,3-Dihydro-3,4-dimethyl-7-hydroxy-4H-1-benzopyran (a precursor ofcompound No. 227)

Resorcinol (5.5 g) and 7.2 g of ethyl 2-methylacetoacetate were stirredat 10° C. for 3 hours in the presence of a catalytic amount concentratedsulfuric acid to give 7.8 g (yield 83%) of3,4-dimethyl-7-hydroxycoumarin. The product was hydrogenated anddehydrated as in Referential Example 16 to give 5.7 g (78%) of thedesired product as a pale brown liquid.

REFERENTIAL EXAMPLE 182,3-Dihydro-4,4-dimethyl-7-hydroxy-4H-1-benzopyran (a precursor ofcompound No. 166)

A mixture of 103 g of resorcinol and 4.6 g of conc. sulfuric acid washeated at 130° C. with stirring, and 58 g of methyl 3,3-dimethylacrylatewas added. The mixture was heated at 130° C. for 3 hours with stirring.The reaction mixture was worked up in a customary manner, and theresidue after concentration was purified by column chromatography togive 24 g (yield 27%) of 4,4-dimethyl-7-hydroxycoumarin (melting point84°-85° C.). The product was worked up in the same way as in ReferentialExample 16 to give 16.8 g (yield 75%) of the desired product ascolorless crystals (melting point 88°-88.5° C.).

REFERENTIAL EXAMPLE 19 2,3-Dihydro-7-hydroxy-2-methyl-4H-1-benzopyran (aprecursor of compound No. 164)

A 100 ml autoclave was charged wtih 20 g of resorcinol, 12 g ofbutadiene, 4 ml of H₃ PO₄ and 60 ml of toluene, and purged withnitrogen. The mixture was then heated at 100° C. for 3.5 hours. Thecrude product was purified by column chromatography to give 24.1 g(yield 82%) of the desired product as a brown liquid.

REFERENTIAL EXAMPLE 202,3-Dihydro-7-hydroxy-2,4,4-trimethyl-4H-1-benzopyran (a precursor ofcompound No. 180)

A 100 ml autoclave was charged with 6.0 g of7-hydroxy-2,4,4-trimethyl-4H-1-benzopyran synthesized by the method ofJapanese Laid-Open Patent Publication No. 5475/1981, 1.0 g of 5%palladium-carbon and 20 ml of ethanol, and hydrogenation was carried outat 85° C. The resulting product was recrystallized from n-hexanetolueneto give 5.2 g (86%) of the desired product as colorless crystals(melting point 97°-98° C.).

REFERENTIAL EXAMPLE 213,4-Dihydro-7-hydroxy-2,2,4-trimethyl-2H-1-benzopyran (a precursor ofcompound No. 184)

7-Hydroxy-2,2,4-trimethyl-2H-1-benzopyran synthesized by the method ofJapanese Laid-Open Patent Publication No. 109779/1982 was hydrogenatedas in Referential Example 20. The product was purified by columnchromatography to give the desired product as colorless liquid in ayield of 83%.

REFERENTIAL EXAMPLE 22 2,3-Dihydro-7-hydroxy-2-isopropyl-4H-1-benzopyran(a precursor of compound No. 216)

Pyrrolidine (14.2 g) was added dropwise at room temperature to a mixtureof 15 g of 4-acetylresorcinol, 14.4 g of isobutyraldehyde and 100 ml oftoluene, and the mixture was stirred at room temperature for 6 hour, andthereafter refluxed for 8 hours. The crude product was purified bycolumn chromatography to give 11.4 g of pale yellow crystals. Thehydroxyl group of the resulting compound was benzylated with benzylbromide, and then the product was reduced with sodium borohydride inmethanol and further dehydrated with p-toluenesulfonic acid in toluene.Then, the product was hydrogenated at room temperature for 13 hours inethanol, in the presence of 5% palladium-carbon. The solvent wasevaporated, and the residue was purified by column chromatography togive 6.5 g (yield 34%) of the desired product as a pale yellow liquid.

REFERENTIAL EXAMPLE 232,3-Dihydro-2,2-dimethyl-7-hydroxy-4-methoxy-4H-1-benzopyran (aprecursor of compound No. 187)

7-Benzyloxy-2,3-dihydro-2,2-dimethyl-4-oxobenzopyran synthesized as inReferential Example 22 was dissolved in 60 ml of methanol, and reducedwith 1.0 g of sodium borohydride at room temperature. The product wasdissolved in 10 ml of tetrahydrofuran, and the solution was addeddropwise to a mixture of 1.0 g of 60% sodium hydride and 5 ml oftetrahydrofuran. After generation of hydrogen ceased, 4.3 g of methyliodide was added dropwise, and the mixture was further stirred for 2.5hours at room temperature. The reaction mixture was extracted with ethylacetate. The extract was concentrated, and the residue was dossolved in30 ml of ethanol and hydrogenated at room temperature for 8 hours in thepresence of 5% palladium-carbon catalyst. The crude product was purifiedby column chromatography to give 2.2 g (yield 58%) of the desiredproduct as a pale brown liquid.

REFERENTIAL EXAMPLE 242,3-Dihydro-4,4-ethylenedioxy-7-hydroxy-2-methyl-4H-1-benzopyran (aprecursor of compound No. 289)

A mixture of 2.2 g of 7-benzyloxy-2,3-dihydro-2-methyl-4-oxobenzopyran,4.5 g of ethylene glycol, 1.8 g of triethyl orthoformate, 80 mg ofp-toluenesulfonic acid and 20 ml of toluene was refluxed for 5.5 hours.The reaction product was purified by column chromatography to give 2.6 gof the acetal. The acetal was hydrogenated at room temperature for 9.5hours in ethanol with 5% palladium-carbon. The hydrogenated product waspurified by column chromatography to give 1.4 g (yield 76%) of thedesired product as pale pink crystals.

REFERENTIAL EXAMPLE 252,3-Dihydro-7-hydroxy-2-methoxy-2-methyl-4H-1-benzopyran (a precursor ofcompound No. 258)

Methyl vinyl ketone (7.7 g) was added dropwise under ice cooling to asolution composed of 11 g of resorcinol, 11.7 g of trimethylorthoformate and 0.1 ml of conc. sulfuric acid. After the addition, themixture was stirred at room temperature for 2 hours. The reactionmixture was neutralized with a saturated aqueous solution of sodiumbicarbonate, and then extracted with ethyl acetate. The residue leftafter evaporation of the solvent as purified by column chromatography togive 12.5 g (yield 70%) of the desired product as colorless crystals(melting point 107°-108° C.).

REFERENTIAL EXAMPLE 26 2,3-Dihydro-2-ethoxy-7-hydroxy-4H-1-benzopyran (aprecursor of compound No. 221)

A solution of 1.6 g of acrolein diethylacetal in 4 ml of ethanol wasadded dropwise under cooling to a solution composed of 1.1 g ofresorcinol, 0.05 g of conc. sulfuric acid and 6 ml of ethanol. Whilemaintaining the temperature at less than 10° C., the mixture was stirredfor 2 hours. The reaction mixture was neutralized with an aqueoussolution of sodium carbonate and extracted with ethyl acetate. Thesolvent was evaporated, and the residue was purified by columnchromatography to give 1.2 g (yield 63%) of the desired product as acolorless liquid.

REFERENTIAL EXAMPLE 272,3-Dihydro-2,3-dimethyl-7-hydroxy-4H-1-benzopyran (a precursor ofcompound No. 239)

Resorcinol (11 g) and 20 g of tiglic acid were heated together with 15 gof zinc chloride at 180° C. for 30 minutes with stirring. After cooling,the reaction mixture was extracted with ethyl acetate. The extract wasconcentrated to give 13 g of crystals. The crystals were benzylated withbenzyl bromide in acetone in the presence of potassium carbonate,dissolved in a mixture of ethanol and tetrahydrofuran, and reduced withsodium borohydride. The reaction product was dehydrated in toluene witha catalytic amount of p-toluenesulfonic acid. The dehydrated product waspurified by column chromatography to give the benzyl ether (colorlessliquid). The liquid was hydrogenated in ethanol at room temperature for15 hours using a 5% palladium-carbon catalyst. The crude product waspurified by column chromatography to give 10.5 g (yield 59%) of thedesired product as a pale yellow liquid.

REFERENTIAL EXAMPLE 282,3-Dihydro-2,4-dimethyl-7-hydroxy-4H-1-benzopyran (a precursor ofcompound No. 230)

Resorcinol (11 g) and 17.2 g of crotonic acid were heated at 180° C. for30 minutes together with 15 g of zinc chloride with stirring. Thereaction mixture was extracted with ethyl acetate, and purified bycolumn chromatography to give 7.3 g of2,3-dihydro-7-hydroxy-2-methyl-4-oxobenzopyran. The OH group of thecompound was benzylated in a customary manner, and then the product wasreacted with CH₃ MgBr in tetrahydrofuran. The product was thenhydrogenated in ethanol at room temperature for 13 hours in the presenceof 5% palladium-carbon. The hydrogenated product was purified by columnchromatography to give 4.2 g (yield 24%) of the desired product as abrown liquid.

REFERENTIAL EXAMPLE 292,3-Dihydro-7-hydroxy-2,2,3-trimethyl-4H-1-benzopyran (a precursor ofcompound No. 275)

A mixture of 5.0 g of2,3-dihydro-2,2-dimethyl-7-hydroxy-4-oxobenzopyran, 3.8 g of 37% aqueousformaldehyde, 10.5 g of potassium hydroxide and 50 ml of ethanol washeated at 50° C. for 3 hours with stirring. The reaction mixture wasacidified with 2N-HCl and extracted with ethyl acetate. The extract waspurified by column chromatography to give 1.8 g of the enone. In acustomary manner, the enone was hydrogenated, and then reacted withbenzyl bromide to give7-benzyloxy-2,3-dihydro-4-oxo-2,2,3-trimethylbenzpyran. The product wasreduced with 2.0 g of sodium borohydride in methanol-tetrahydrofuran,and then dehydrated in toluene using 0.1 g of p-toluenesulfonic acid.This compound was hydrogenated in a customary manner to give 1.4 g(yield 27%) of the desired product as a pale brown liquid.

REFERENTIAL EXAMPLE 30 2,3-Dihydro-7-hydroxy-4-methoxy-4H-1-benzopyran(a precursor of compound No. 211)

Under ice cooling, AlCl₃ (3 molar equivalent) was added little by littleto a solution composed of 11 g of resorcinol, 12.7 g of2-chloropropionyl chloride and 120 ml of nitrobenzene. After theaddition, the mixture was heated at 40° to 50° C. for 4 hours withstirring. The reaction mixture was worked up and purified in a customarymanner to give 4.1 g of 2,3-dihydro-7-hydroxy-4-oxobenzopyran. Theresulting compound was benzylated, reduced with sodium borohydride inmethanol, and then methylated with methyl iodide in tetrahydrofuran inthe presence of sodium hydride. In a customary manner, the methylatedproduct was hydrogenated to give 1.7 g (yield 9.4%) of the desiredproduct as a colorless liquid.

REFERENTIAL EXAMPLE 31 2,3-Dihydro-6-hydroxy-2-methyl-4H-1-benzopyran (aprecursor of compound No. 320)

Referential Example 19 was repeated except that hydroquinone was usedinstead of resorcinol. There was obtained the desired product as acolorless liquid (yield 65%; b. p. 160°-162° C./12 mm).

REFERENTIAL EXAMPLE 322,3-Dihydro-6-hydroxy-2-methoxy-2-methyl-4H-1-benzopyran (a precursor ofcompound No. 332)

Referential Example 25 was repeated except that hydroquinone was usedinstead of resorcinol. Pale brown crystals were obtained in a yield of36%.

REFERENTIAL EXAMPLE 332,3-Dihydro-4,4-dimethyl-6-hydroxy-4H-1-benzopyran (a precursor ofcompound No. 329)

A mixture of 8.8 g of hydroquinone, 5 g of methyl 3,3-dimethylacrylateand 0.4 g of conc. sulfuric acid was heated at 130° C. for 4 hours. Thereaction mixture was cooled, and then 15 ml of toluene was added. Thecrystals that precipitated were separated by filtration. The filtratewas concentrated and then distilled under reduced pressure to give 4.6 g(yield 70%) of 3,4-dihydro-4,4-dimethyl-6-hydroxycoumarin as pale pinkcrystals (melting point 95°-96° C.). The crystals (3.0 g) were dissolvedin 10 ml of tetrahydrofuran, and the solution was added dropwise at roomtemperature to a mixture of 0.9 g of lithium aluminum hydride and 20 mlof tetrahydrofuran. The mixture was then refluxed for 4 hours. Thereaction mixture was worked up in a customary manner, and the crudeproduct, without purification, was dissolved in 30 ml of toluene. Acatalytic amount of p-toluenesulfonic acid was added to the solution,and the mixture was heated at 120° C. for 1.5 hours. In a customarymanner, the reaction mixture was worked up, and the residue afterconcentration was isolated and purified by column chromatography to give2.4 g (yield 85%) of the desired product as a yellow orange liquid.

REFERENTIAL EXAMPLE 34 5-Hydroxy-2-isopropylbenzofuran (a precursor ofcompound No. 334)

In accordance with Referential Example 10, 5.0 g of an adduct wassynthesized from p-quinone and 3-methyl-2-morpholino-1-butene, andstirred together with 150 ml of 4N-HCl at room temperature for 16 hours.The reaction mixture was worked up in a customary manner, and purifiedby column chromatography to give 1.6 g (yield 49%) of the desiredproduct as a yellowish orange liquid.

REFERENTIAL EXAMPLE 35 3-Ethyl-5-hydroxybenzofuran (a precursor ofcompound No. 339)

The captioned compound was synthesized by the method of ReferentialExample 11.

REFERENTIAL EXAMPLE 36 2,3-Dihydro-7-hydroxy-2-methylbenzofuran (aprecursor of compound No. 346)

A mixture of 10.7 g of catechol, 17.3 g of catechol diacetate, 34.5 g ofpotassium carbonate, 30.3 g of allyl bromide and 200 ml of acetone wasrefluxed for 5 hours. The reaction mixture was filtered, and thefiltrate was concentrated and purified by column chromatography to give26.5 g (yield 71%) of 2-acetoxyphenyl allyl ether as a pale yellowliquid. Ten grams of this liquid was heated at 220° to 230° C. for 1.5hours. After cooling, the reaction mixture was purified by columnchromatography to give 6.5 g (yield 65%) of 2-acetoxy-6-allylphenol as apale yellow liquid. Then, 3.0 g of this liquid and 12 ml of an aceticacid solution of 25% hydrobromic acid were reacted at 70° C. for 6hours. The reaction mixture was poured into ice water, neutralized withan aqueous solution of sodium bicarbonate, and extracted with ethylacetate. The concentrate was hydrolyzed with potassium hydroxide andaqueous ethanol, and worked up in a customary manner. The product wasthen purified by column chromatography to give 0.7 g (yield 31%) of thedesired product as a pale yellow liquid.

REFERENTIAL EXAMPLE 372,3-Dihydro-2,2-dimethyl-8-hydroxy-4H-1-benzopyran (a precursor ofcompound No. 353)

While a mixture of 10 g of catechol, 50 ml of p-xylene, 25 ml of hexane,1 ml of phosphoric acid and 0.3 ml of water was heated at 100° C., 7.3 gof isoprene was added dropwise over 10 minutes, and the reaction wasfurther carried out for 7 hours. After cooling, the resultingprecipitate was separated by filtration. The filtrate was concentrated,and purified by column chromatography to give 1.7 g (yield 11%) of theproduct as a pale pink liquid.

REFERENTIAL EXAMPLE 38 2,2-Dimethyl-4-hydroxybenzodioxolane (a precursorof compound No. 355)

A mixture of 9.0 g of pyrogallol, 7.5 g of 2,2-dimethoxypropane and 100ml of toluene was refluxed for 4.5 hours. After cooling, the reactionmixture was worked up in a customary manner and purified by columnchromatography to give 2.0 g (yield 17%) of the desired product as apale yellow solid.

REFERENTIAL EXAMPLE 392,3-Dihydro-2,2-dimethyl-7-(4-nitrophenoxy)-4H-1-benzopyran (anintermediate of compound No. 172)

2,3-Dihydro-2,2-dimethyl-7-hydroxy-4H-1-benzopyran (2.0 g) synthesizedas in Referential Example 19, 1.8 g of p-chloronitrobenzene, 0.9 g ofpotassium hydroxide, 20 ml of N,N-dimethylformamide and 10 ml of toluenewere put into a flask equipped with the DeanStark condenser, and wereheated to 110° C. While removing evaporated water as an azeotrope withtoluene, the reaction was carried out for 1 hour. After cooling, thereaction mixture was poured into water, and extracted with ethylacetate. The extract was dried over magnesium sulfate, and the solventswere evaporated. The residue was purified by column chromatography togive 2.8 g (yield 84%) of the desired product as a brown liquid.

REFERENTIAL EXAMPLE 404-(2,3-Dihydro-2,2-dimethyl-4H-1-benzopyran-7-yl)oxyaniline (anintermediate of compound No. 172)

To 2.7 g of the nitrobenzene derivative obtained in Referential Example39 were added 0.3 g of 5% palladium-carbon and 20 ml of ethanol, and themixture was stirred at 40° to 50° C. for 5 hours in an atmosphere ofhydrogen. The catalyst was separated by filtration, and the filtrate wasconcentrated to give 1.8 g (yield 72%) of the desired product as a graypowder.

REFERENTIAL EXAMPLE 412-(2,3-Dihydro-2,2-dimethyl-4H-1-benzopyran-7-yl)oxy-5-nitropyridine (anintermediate of compound No. 169)

Five milliliters of an N,N-dimethylformamide solution of 1.5 g of2,3-dihydro-2,2-dimethyl-7-hydroxy-4H-1-benzopyran synthesized by themethod of Referential Example 19 was added dropwise to a mixture of 0.35g of sodium hydride and 4 ml of N,N-dimethylformamide. The mixture wasstirred at room temperature for 0.5 hour, and 6 ml of anN,N-dimethylformamide solution of 2-chloro-5-nitropyridine (1.3 g) wasadded to the resulting reddish orange solution, and the mixture wasstirred at room temperature for 5 hours. The reaction mixture was pouredinto 100 ml of water, and extracted with 100 ml of ethyl acetate. Theextract was dried over magnesium sulfate, and concentrated. The residuewas purified by column chromatography to give 2.1 g (yield 84%) of thedesired product as a yellow liquid.

REFERENTIAL EXAMPLE 425-Amino-2-(2,3-dihydro-2,2-dimethyl-4H-1-benzopyran-7-yl)oxypyridine (anintermediate of compound No. 169)

The nitro compound obtained in Referential Example 41 (2.1 g) wasdissolved in 11 ml of ethyl acetate, and 0.11 g of 5% palladium-carbonwas added. Hydrogenation was carried out in accordance with the methodof Referential Example 40. The filtrate was concentrated to give 1.9 g(yield 100%) of the desired product as a pale pink solid (melting point93°-94° C.).

REFERENTIAL EXAMPLE 437-(4-Nitrophenoxy)-2,4,4-trimethyl-4H-1-benzopyran (an intermediate ofcompound No. 194)

One hundred grams of 7-hydroxy-2,4,4-trimethyl-4H-1-benzopyran(synthesized by the method of Japanese Laid-Open Patent Publication No.5475/1981), 79 g of p-chloronitrobenzene, 42 g of potassium hydroxide,500 ml of N,N-dimethylformamide and 500 ml of toluene were introducedinto a flask equipped with the Dean-Stark condenser, and heated at 110°to 116° C. While removing the distilled water as an azeotrope withtoluene, the mixture was stirred for 2 hours. The reaction mixture wascooled to room temperature, and 1 liter of water, 500 ml of ethylacetate and 120 ml of 2N-HCl were added. The insoluble materials wereseparated by filtration. The filtrate was subjected to oil-waterseparation. The oil layer was washed with 500 ml of brine, and driedover magnesium sulfate. The solvent was evaporated. Methanol (650 ml)was added to the residue, and crystals that precipitated were collected,washed with 650 ml of hexane, and dried to give 106 g (yield 67%) of thedesired product as a brown powder (melting point 80° C.).

REFERENTIAL EXAMPLE 442,3-Dihydro-2-methoxy-7-(4-nitrophenoxy)-2,4,4-trimethyl-4H-1-benzopyran(an imtermediate of compound No. 194)

A mixture of the 7-(4-nitrophenoxy)-2,4,4-trimethyl-4H-1-benzopyranobtained in Referential Example 43, 66 ml of methanol, 0.7 g ofAmberlyst-15 and 6 ml of toluene was stirred for 4.5 hours, andAmberlyst-15 was separated by filtration. The filtrate was concentrated,and 30 ml of methanol was added. Crystals that precipitated werecollected by filtration, washed with 50 ml of methanol, and dried togive 6.7 g (90%) of the desired product as a white powder (melting point125° C.).

REFERENTIAL EXAMPLE 457-(4-Aminophenoxy)-2,3-dihydro-2-methoxy-2,4,4-trimethyl-4H-1-benzopyran(an intermediate of compound No. 194)

A mixture of 6.7 g of the2,3-dihydro-2-methoxy-7-(4-nitrophenoxy)-2,4,4-trimethyl-4H-1-benzopyranobtained in Referential Example 44, 0.7 g of 5% palladium-carbon, and 67ml of ethyl acetate was stirred at room temperature for 5.5 hours in anatmosphere of hydrogen. Palladium-carbon was separated by filtration,and the filtrate was concentrated to give 6.0 g (yield 98%) of thedesired product as a yellow liquid.

REFERENTIAL EXAMPLE 462,3-Dihydro-2-hydroxy-7-(4-nitrophenoxy)-2,4,4-trimethyl-4H-1-benzopyran(an intermediate of compound No. 319)

A mixture of 6.5 g of the7-(4-nitrophenoxy)-2,4,4-trimethyl-4H-1-benzopyran, 26 ml of water, 13ml of conc. hydrochloric acid and 65 ml of acetone was refluxed for 2hours. An 10% aqueous solution of sodium hydroxide was added to thereaction mixture to neutralize it, and then 100 ml of water and 200 mlof ethyl acetate were added, and the mixture was subjected to oil-waterseparation. The oil layer was washed with 50 ml of brine, dried overmagnesium sulfate and concentrated. Toluene (5 ml) and 45 ml of hexanewas added to the residue, and the precipitated crystals were collectedby filtration, washed with 50 ml of hexane and dried to give 5.1 g(yield 70%) of a pale brown powder (mp. 159°-160° C., recrystallizedfrom ethanol).

REFERENTIAL EXAMPLE 477-(4-Aminophenoxy)-2,3-dihydro-2-hydroxy-2,4,4-trimethyl-4H-1-benzopyran(an intermediate of compound No. 319)

A mixture of 5.0 g of7-(4-nitrophenoxy)-2,4,4-trimethyl-4H-1-benzopyran, 0.5 g of 5%palladium-carbon and 50 ml of ethyl acetate was stirred at roomtemperature for 5.5 hours in an atmosphere of hydrogen. Thepalladium-carbon was separated by filtration, and the filtrate wasconcentrated. The residue was recrystallized from ethyl acetate-hexaneto give 4.3 g (yield 93%) of the desired product as a white powder.

REFERENTIAL EXAMPLE 487-(4-Aminophenoxy)-2,3-dichloromethano-2,3-dihydro-2,4,4-trimethyl-4H-1-benzopyran(an intermediate of compound No. 309)

A solution of 0.02 g of benzyltrimethylammonium chloride in 5 ml ofchloroform was added dropwise to a mixture of 1.6 g of7-(4-nitrophenoxy)-2,4,4-trimethyl-4H-1-benzopyran, 20 ml of chloroformand 0.7 g of sodium hydroxide with stirring at 5° C. The mixture wasstirred at room temperature for 2 hours, poured into ice watercontaining dilute hydrochloric acid, and extracted with dichloromethane.The extract was washed with brine, dried over sodium sulfate, andconcentrated. Ethyl acetate (30 ml) and 5% palladium-carbon were addedto the residue, and the mixture was stirred at 60° C. for 5 hours in anatmosphere of hydrogen. The palladium-carbon was removed by filtration,and the filtrate was concentrated. The residue was purified by columnchromatography and recrystallization (dichloromethane-hexane) to give0.74 g (yield 40%) of the desired product as colorless crystals (meltingpoint 46° to 147° C.).

REFERENTIAL EXAMPLE 49 4-(2,3-Dihydro-2,2-dimethyl-4H-1-benzopyran-7-yl)oxyphenyl isocyanate (an intermediate of compoundNo. 172)

A solution of 8.1 g (0.03 mole) of the aniline derivative obtained bythe method of Referential Example 40 was added dropwise at 0° C. to 60ml of ethyl acetate into which 0.12 mole of phosgene had been blown, andthe mixture was stirred for 0.5 hour. Thereafter, the mixture wasrefluxed for 1 hour, and the excess of phosgene was replaced by nitrogengas. The ethyl acetate was evaporated under reduce pressure to give 8.7g (yield 98%) of the desired product as a yellow orange liquid (IR: 2260cm⁻¹).

The following Example illustrates the synthesis of typical examples ofthe compounds of formula [I] and their properties.

COMPOUND NO. 11,1-dimethyl-3-[2-(3-methyl-2,3-dihydro-6-benzofuryloxy)pyridin-5-yl]urea

2-(3-Methyl-2,3-dihydro-6-benzofuryloxy)-5-aminopyridine (0.5 g) wasdissolved in 2.5 ml of pyridine, and a solution of composed 0.27 g ofdimethylcarbamoyl chloride and 2.5 ml of toluene was added. A solutioncomposed of 0.27 g of diethylcarbamoyl chloride and 2.5 ml of toluenewas added, and the mixture was stirred at room temperature for 9 hours.Water and ethyl acetate were added to the reaction mixture, and theorganic layer was separated. The organic layer was washed with asaturated aqueous solution of sodium chloride, and dried over anhydrousmagnesium sulfate. Ethyl acetate was evaporated under reduced pressure,and the precipitated crystals were washed with n-hexane to give 0.63 g(yield 96%) of the desired product as pale brown crystals.

Melting point: 153°-154° C.

Mass spectrum: m/Z 313 (molecular ion peak).

IR spectrum (KBr disk; cm⁻¹) 3260, 3050, 2958, 1637, 1602, 1357, 1274,1237, 1133, 979, 850, 842, 760.

¹ H-NMR spectrum (CDCl₃ solution; ppm) ##STR520## (a) 1.31 (3H, d, J=7.2Hz), (b) 3.00 (6H, s), (c) 3.28 (1H, m), (d) 4.09 (1H, t, J=7.2 Hz), (e)4.71 (1H, t, J=7.2 Hz), (f) 6.51 (1H, d, J=2.7 Hz), (g) 6.57 (1H, dd,J=2.7, 7.2 Hz), (h) 6.70 (1H, brs), (i) 6.92 (1H, d, J=9.0 Hz), (j) 7.08(1H, d, J=7.2 Hz), (k) 7.91 (1H, dd, J=2.7, 9.0 Hz), (l) 8.02 (1H, d,J=2.7 Hz).

COMPOUND NO. 3311-methyl-3-[4-(2-methoxy-2-methyl-2,3-dihydro-6-benzopyranyloxy)phenyl]urea

Methyl isocyanate (0.16 g) was added at room temperature to a solutioncomposed of 0.4 g of4-(2-methoxy-2-methyl-2,3-dihydro-6-benzopyranyloxy)aniline and 3.0 mlof toluene, and the mixture was stirred for 6 hours. Addition ofn-hexane to the mixture yielded crystals which were collected byfiltration to give the desired product as white crystals (yield not lessthan 97%).

Melting point: 140°-140.5° C.

Mass spectrum: m/Z 342 (molecular ion peak).

IR spectrum (KBr disk; cm⁻¹) 3330, 2950, 1642, 1605, 1586, 1505, 1486,1212, 1092, 1058, 918, 872.

¹ H-NMR spectrum (CDCl₃ solution; ppm) ##STR521## (a) 1.54 (3H, s), (b)1.68-2.24 (2H, m), (c) 2.32-3.28 (2H, m), (d) 2.75 (3H, d, J=5.4), (e)3.28 (3H, s), (f) 5.43 (1H, d, J=5.4), (g) 6.60-7.40 (8H, m).

COMPOUND NO. 1721,1-Dimethyl-3-[4-(2,2-dimethyl-2,3-dihydro-7-benzopyranyloxy)phenyl]urea

A solution of 0.5 g of4-(2,2-dimethyl-2,3-dihydro-6-benzopyranyloxy)phenyl isocyanate in 2.5ml of toluene was added dropwise at 0° C. to a solution of 0.2 g ofdimethylamine in 3 ml of toluene, and the mixture was then stirred atroom temperature for 2 hours. Toluene was evaporated under reducedpressure, and the precipitated crystals were washed with n-hexane togive 0.62 g (yield 97%) of the desired product as white crystals.

Melting point: 137°-138° C.

Mass spectrum: m/Z 340 (molecular ion peak).

IR spectrum (KBr disk; cm⁻¹) 3310, 3040, 2940, 1640, 1602, 1370, 1210,1147, 996, 838, 813.

¹ H-NMR spectrum (CDCl₃ solution; ppm) ##STR522## (a) 1.30 (6H, s), (b)1.77 (2H, t, J=7.2 Hz), (c) 2.72 (2H, t, J=7.2 Hz), (d) 3.02 (6H, s),(e) 6.33 (1H, brs), (f) 6.39 (1H, d, J=2.7 Hz), (g) 6.47 (1H, dd, J=2.7,7.2 Hz), (h) 6.96 (2H, d, J=9.0 Hz), (i) 6.97 (1H, d, J=7.2 Hz), (j)7.34 (2H, d, J=9.0 Hz).

Other compounds of formula [I] shown in Tables 1 to 11 were synthesizedin accordance with the method used to produce compound No. 1 or No. 331,and the results are shown in Table 13. The NMR spectra were measured inCDCl₃. The IR spectra of solid compounds were measured using KBr disks,and those of liquid compounds were measured at neat.

                                      TABLE 13                                    __________________________________________________________________________    Compound                                                                            Yield                                                                             Melting point                                                       No.   (%) (°C.)                                                                         Spectral data                                                __________________________________________________________________________    2     94  153-154                                                                              IR: 3280 (ν.sub.NH), 1672 (ν.sub.c=o).                 3     not less                                                                          114-115                                                                   than 97                                                                 4     85  155-156                                                                              IR: 3310 (ν.sub.NH), 1642 (ν.sub.c=o).                 5     not less                                                                          110.5-112                                                                            NMR:                                                                              1.31 (3H, d, J=7.2), 3.18 (3H, s), 3.29 (1H, m),                              3.76                                                           than 97        (3H, s), 4.70 (1H, t, J=9.0), 5.09 (1H, dd, J=7.2,                            9.0), 6.36-7.12 (3H, m), 6.96 (2H, d, J=9.0), 7.43                            (2H, d, J=9.0).                                          6     81  145-147                                                                              NMR:                                                                              1.22 (3H, d, J=8.1), 1.28 (3H, s), 1.47 (3H, s),                              2.98                                                                          (6H, s), 3.05 (1H, q, J=8.1), 6.24 (1H, d, J=2.7),                            6.54 (1H, dd, J=2.7, 7.2), 6.81 (1H, d, J=9.0),                               7.03                                                                          (1H, d, J=7.2), 7.90 (1H, dd, J=2.7, 9.0), 8.03                               (1H, d, J=2.7).                                          7     94  94-95  NMR:                                                                              1.22 (3H, d, J=7.2), 1.30 (3H, s), 1.49 (3H, s),                              3.16 (1H, q, J=7.2), 3.22 (3H, s), 3.78 (3H, s),                              6.50                                                                          (1H, d, J=2.7), 6.58 (1H, dd, J=2.7, 8.1), 6.88 (1H,                          d,                                                                            J=9.0), 7.06 (1H, d, J=8.1), 7.80 (1H, brs), 8.04                             (1H, dd, J=2.7, 9.0), 8.16 (1H, d, J=2.7).               8     not less                                                                          146-148                                                                   than 97                                                                 9     95  121-123                                                                              IR: 3310 (ν.sub.NH), 1643 (ν.sub.c=o).                 10    89  117-120                                                                              IR: 3350 (ν.sub.NH), 1667 (ν.sub.c=o).                 11    94  142-144                                                                              NMR:                                                                              3.04 (6H, s), 3.18 (2H, t, J=7.2), 4.60 (2H, t,                               J=7.2),                                                                       6.32 (1H, s), 6.50 (2H, m), 6.94 (2H, d, J=9.0),                              7.10 (1H, dd, J=2.7, 7.2), 7.36 (2H, d, J=9.0).          12    91  124-126                                                                              NMR:                                                                              3.14 (2H, t, J=7.2), 3.20 (3H, s), 3.78 (3H, s),                              4.60 (2H, t, J=7.2), 6.44 (2H, m), 6.98 (2H, d,                               J=9.0),                                                                       7.18 (1H, dd, J=2.7, 7.2), 7.42 (2H, d, J=9.0),                               7.86 (1H, s).                                            13    not less                                                                          143.5-145                                                                            IR: 3310 (ν.sub.NH), 1642 (ν.sub.c=o).                       than 97    NMR:                                                                              0.96 (3H, t, J=7.2), 1.69 (2H, q, J=7.2), 3.02 (6H,                           s),                                                                           3.31 (1H, m), 4.24 (1H, t, J=9.0), 4.65 (1H, t,                               J=9.0),                                                                       6.32-7.48 (8H, m).                                       14    not less                                                                          liquid IR: 3330 (ν.sub.NH), 1676 (ν.sub.c=o).                       than 97                                                                 15    not less                                                                            129-129.9                                                                          IR: 3290 (ν.sub.NH), 1635 (ν.sub.c=o).                       than 97                                                                 16    85    58-59.0                                                                            IR: 3310 (ν.sub.NH), 1660 (ν.sub.c=o).                 17    53    198-199.5                                                         18    not less                                                                          101-103                                                                   than 97                                                                 19    not less                                                                          152-153                                                                              NMR:                                                                              1.48 (3H, d, J=7.2), 2.76 (1H, dd, J=8.0, 15.0),               than 97        2.85 (3H, d, J=5.4), 3.28 (1H, d, J=8.0, 15.0),                               4.94 (1H, m), 6.44 (2H, m), 6.94 (2H, d, J=9.0),                              7.08 (1H, d, J=8.0), 7.24 (2H, d, J=9.0).                20    not less                                                                          124-128                                                                              NMR:                                                                              1.47 (3H, d, J=7.2), 2.74 (1H, dd, J=8.0, 15.0),               than 97        3.06 (6H, s), 3.30 (1H, dd, J=8.0, 15.0),                                     4.94 (1H, m), 6.40 (2H, m), 6.94 (2H, d, J=9.0),                              7.06 (1H, d, J=8.0), 7.36 (2H, d, J=9.0).                21    64  75-76  NMR:                                                                              1.48 (3H, d, J=7.2), 2.75 (1H, dd, J=8.0, 15.0),                              3.24 (3H, s), 3.30 (1H, dd, J=8.0, 15.0), 3.80                                (3H, s), 4.94 (1H, m), 6.40 (2H, m), 6.98 (2H, d,                             J=                                                                            9.0), 7.06 (1H, d, J=8.0), 7.42 (2H, d, J=9.0).          22    not less                                                                          138-140                                                                              NMR:                                                                              1.04 (3H, t, J=7.2), 1.76 (2H, m), 2.82 (1H, dd,                              J=8.0,                                                         than 97        15.0), 2.88 (3H, d, J=5.4), 3.26 (1H, dd, J=8.0,                              15.0), 4.74 (1H, m), 6.46 (2H, m), 6.98 (2H, d, J=                            9.0), 7.08 (1H, d, J=8.0), 7.26 (2H, d, J=9.0).          23    not less                                                                          132-136                                                                              NMR:                                                                              1.04 (3H, t, J=7.2), 1.80 (2H, m), 2.82 (1H, dd,                              J=8.0,                                                         than 97        15.0), 3.08 (6H, s), 3.24 (1H, dd, J=8.0, 15.0),                              4.72 (1H, m), 6.40 (2H, m), 6.94 (2H, d, J=9.0),                              7.06 (1H, d, J=8.0), 7.34 (2H, d, J=9.0).                24    75   98-100                                                                              NMR:                                                                              1.04 (3H, t, J=7.2), 1.80 (2H, m), 2.80 (1H, dd,                              J=8.0,                                                                        15.0), 3.18 (3H, s), 3.26 (1H, dd, J=8.0, 15.0),                              4.70 (1H, m), 6.40 (2H, m), 6.94 (2H, d, J=9.0),                              7.06 (1H, d, J=8.0), 7.42 (2H, d, J=9.0).                25    not less                                                                          155-156                                                                              NMR:                                                                              0.98 (3H, d, J=7.2), 1.06 (3H, d, J=7.2), 1.92 (1H,                           m),                                                            than 97        2.84 (3H, s), 2.86 (1H, dd, J=8.0, 15.0), 3.16 (1H,                           dd, J=8.0, 15.0), 4.54 (1H, m), 6.44 (2H, m), 6.94                            (2H, d, J=9.0), 7.06 (1H, d, J=8.0), 7.24 (2H, d,                             J=9.0).                                                  26    not less                                                                          148-150                                                                              NMR:                                                                              0.98 (3H, d, J=7.2), 1.06 (3H, d, J=7.2), 1.92 (1H,                           m),                                                            than 97        2.86 (1H, dd, J=8.0, 15.0), 3.14 (1H, dd, J=8.0,                              15.0),                                                                        3.08 (6H, s), 4.54 (1H, m), 6.42 (2H, m), 6.94 (2H,                           d,                                                                            J=9.0), 7.06 (1H, d, J=7.2), 7.34 (2H, d, J=9.0).        27    87  115.5-116.5                                                                          NMR:                                                                              0.98 (3H, d, J=7.2), 1.06 (3H, d, J=7.2), 1.94 (1H,                           m),                                                                           2.88 (1H, dd, J=8.0, 15.0), 3.18 (1H, dd, J=8.0,                              15.0), 3.22 (3H, s), 3.80 (3H, s), 4.54 (1H, m),                              6.44 (2H, m), 6.94 (2H, d, J=9.0), 7.06 (1H, d,                               J=7.2),                                                                       7.42 (2H, d, J=9.0).                                     28    94  144-145                                                                              NMR:                                                                              0.94 (3H, t, J=7.2), 1.00 (3H, d, J=7.2), 1.70 (3H,                           m),                                                                           2.84 (3H, brs), 2.80-3.20 (2H, m), 4.70 (1H, m),                              6.40 (2H, m), 6.94 (2H, d, J=9.0), 7.04 (1H, d,                               J=8.0),                                                                       7.22 (2H, d, J=9.0).                                     29    85  142-144                                                                              NMR:                                                                              0.94 (3H, t, J=7.2), 1.00 (3H, d, J=7.2), 1.60 (3H,                           m),                                                                           2.70-3.30 (2H, m), 3.04 (6H, s), 4.64 (1H, m),                                6.40 (2H, m), 6.94 (2H, d, J=9.0), 7.06 (1H, d,                               J=8.0),                                                                       7.14 (2H, d, J=9.0).                                     30    79  89-90  NMR:                                                                              0.94 (3H, t, J=7.2), 1.00 (3H, d, J=7.2), 1.70 (3H,                           m),                                                                           2.80-3.20 (2H, m), 3.20 (3H, s), 3.78 (3H, s),                                4.64 (1H, m), 6.40 (2H, m), 6.94 (2H, d, J=9.0),                              7.04 (1H, d, J=8.0), 7.42 (2H, d, J=9.0).                31    90  139-140                                                                              IR: 3310 (ν.sub.NH), 1634 (ν.sub.c=o).                 32    86  162.5-163                                                                            IR: 3290 (ν.sub.NH), 1636 (ν.sub.c=o).                 33    90  118-119                                                                              IR: 3340 (ν.sub.NH), 1665 (ν.sub.c=o).                 34    63  liquid NMR:                                                                              0.95 (3H, t, J=7.0), 1.41 (3H, s), 1.70 (2H, q,                               J=7.0),                                                                       2.76 (3H, d, J=5.0), 2.94 (2H, d, J=6.0), 5.62 (1H,                           d,                                                                            J= 6.0), 6.34-6.50 (2H, m), 6.80-7.10 (3H, m),                                7.16-7.36 (2H, m), 7.52 (1H, brs).                       35    71  liquid NMR:                                                                              0.94 (3H, t, J=7.0), 1.40 (3H, s), 1.72 (2H, q,                               J=7.0),                                                                       2.94 (2H, s), 3.00 (6H, s), 6.34-6.48 (2H, m),                                6.86-7.60 (4H, m), 7.22-7.40 (2H, m).                    36    85  liquid NMR:                                                                              0.94 (3H, t, J=7.0), 1.41 (3H, s), 1.72 (2H, q,                               J=7.0),                                                                       2.92 (2H, d, J=6.0), 3.16 (3H, s), 3.74 (3H, s),                              6.36-6.50 (2H, m), 6.90-7.10 (3H, m), 7.26-7.50 (2H,                          .                                                                             m), 7.70 (1H, brs).                                      37    85  78-81  NMR:                                                                              0.90 (6H, t, J=7.0), 1.68 (4H, q, J=7.0), 2.76 (3H,                           d,                                                                            J=5.0), 2.91 (2H, s), 5.36 (1H, brs), 6.24-6.44                               (2H,                                                                          m), 6.80-7.05 (3H, m), 7.10-7.30 (2H, m).                38    65  liquid NMR:                                                                              0.90 (6H, t, J=7.0), 1.68 (4H, q, J=7.0), 2.95 (2H,                           s),                                                                           2.98 (6H, s), 6.30-6.50 (3H, m), 6.88-7.04 (3H, m),                           7.20-7.36 (2H, m).                                       39    65  liquid NMR:                                                                              0.90 (6H, t, J=7.0), 1.70 (4H, q, J=7.0), 2.90 (2H,                           s),                                                                           3.16 (3H, s), 3.72 (3H, s), 6.30-6.44 (2H, m),                                6.88-7.04 (3H, m), 7.34-7.46 (2H, m), 7.65 (1H,                               brs).                                                    40    not less                                                                          118.5-119.5                                                               than 97                                                                 41    not less                                                                          liquid NMR:                                                                              0.90 (3H, t, J=7.2), 1.13 (3H, d, J=6.3), 1.16 (3H,                           s),                                                            than 97        1.68 (2H, q, J=7.2), 2.89 (6H, s), 3.08 (1H, q,                               J=6.3),                                                                       6.28-7.08 (4H, m), 7.50-8.04 (3H, m).                    42    not less                                                                          liquid NMR:                                                                              1.00 (3H, t, J=7.2), 1.23 (3H, d, J=6.3), 1.26 (3H,                           s),                                                            than 97        1.79 (2H, q, J=7.2), 3.20 (3H, s), 3.23 (1H, q,                               J=6.3),                                                                       3.78 (3H, s), 6.40-7.12 (4H, m), 7.50-8.20 (3H, m).      43    86  81-86  NMR:                                                                              0.98 (3H, t, J=7.2), 1.20 (3H, d, J=6.3), 1.24 (3H,                           s),                                                                           1.75 (2H, q, J=7.2), 3.02 (6H, s), 3.10 (1H, q,                               J=6.3),                                                                       6.37 (1H, d, J=2.7), 6.42 (1H, d, J=2.7, 9.0),                                6.94 (2H, d, J=9.0), 6.98 (1H, d, J=9.0),                                     7.30 (2H, d, J=9.0).                                     44    91    75-76.5                                                           45    88  59.5-60.5                                                           46    64  129-130                                                                              NMR:                                                                              0.99 (3H, t, J=7.2), 1.22 (3H, d, J=6.3), 1.25 (3H,                           s),                                                                           1.78 (2H, q, J=7.2), 3.03 (6H, s), 3.18 (1H, q,                               J=6.3),                                                                       6.33 (1H, d, J=2.7), 6.38 (1H, dd, J=2.7, 9.0),                               6.62 (1H, brs), 6.94 (1H, d, J=9.0), 6.97 (1H, d,                             J=                                                                            9.0), 7.24 (1H, dd, J=2.7, 9.0), 7.58 (1H, d,                                 J=2.7).                                                  47    93  liquid NMR:                                                                              1.00 (3H, t, J=7.2), 1.23 (3H, d, J=6.3), 1.26 (3H,                           s),                                                                           1.78 (2H, q, J=7.2), 3.18 (1H, q, J=6.3), 3.20 (3H,                           s),                                                                           3.78 (3H, s), 6.33 (1H, d, J=2.7), 6.39 (1H, dd,                              J=2.7,                                                                        9.0), 6.99 (2H, d, J=9.0), 7.32 (1H, dd, J=2.7,                               9.0),                                                                         7.69 (1H, d, J=2.7), 7.77 (1H, brs).                     48    59  118.5-119.5                                                                          IR: 3320 (ν.sub.NH), 1642 (ν.sub.c=o), 1520                                 (ν.sub.NO.sbsb.2), 1343 (ν.sub.NO.sbsb.2).         49    60    114-115.5                                                                          IR: 3410 (ν.sub.NH), 3305 (ν.sub.NH), 1648                                  (ν.sub.c=o), 1525 (ν.sub.NO.sbsb.2),                                    1345 (ν.sub.NO.sbsb.2).                               50    70  liquid IR: 3380 (ν.sub.NH), 1670 (ν.sub.c=o), 1525                                 (ν.sub.NO.sbsb.2), 1345 (ν.sub.NO.sbsb.2).         51    92  77-79                                                               52    80  50-51                                                               53    not less                                                                          liquid NMR:                                                                              0.99 (3H, t, J=7.2), 1.22 (3H, d, J=6.3), 1.26 (3H,                           s),                                                            than 97        1.78 (2H, q, J=7.2), 3.19 (1H, q, J=6.3), 3.21 (3H,                           s),                                                                           3.78 (3H, s), 6.41 (1H, d, J=2.7), 6.45 (1H, dd,                              J=2.7,                                                                        9.0), 6.98 (1H, d J=9.0), 7.01 (1H, d, J=8.1),                                7.64 (1H, dd, J=2.7, 8.1), 7.76 (1H, d, J=2.7),                               7.80 (1H, brs).                                          54    not less                                                                          112-113                                                                   than 97                                                                 55    not less                                                                          125.5-126                                                                            IR: 3310 (ν.sub.NH), 1643 (ν.sub.c=o).                       than 97                                                                 56    80    107-108.5                                                                          IR: 3340 (ν.sub.NH), 1660 (ν.sub.c=o).                 57    84  111.5-112                                                                            IR: 3310 (ν.sub.NH), 1650 (ν.sub.c=o).                 58    not less                                                                          liquid IR: 3320 (ν.sub.NH), 1674 (ν.sub.c=o).                       than 97                                                                 59    94    141-142.5                                                                          NMR:                                                                              1.48 (3H, d J=6.3), 2.80-3.40 (2H, m), 3.03 (6H,                              s),                                                                           4.90 (1H, m), 6.40-6.98 (4H, m), 7.80-8.04 (2H, m).      60    65  108-110                                                                              NMR:                                                                              1.48 (3H, d, J=6.3), 2.82 (1H, dd, J=8.1, 9.0),                               3.10 (3H, s), 3.78 (3H, s), 4.96 (1H, m), 6.72-7.00                           (4H, m), 7.70 (1H, brs), 7.93 (1H, dd, J=3.6, 8.1),                           8.12 (1H, d, J=3.6).                                     61    84  159-161                                                                              IR: 3305 (ν.sub.NH), 1640 (ν.sub.c=o).                 62    not less                                                                          128-129                                                                              IR: 3305 (ν.sub.NH), 1660 (ν.sub.c= o).                      than 97                                                                 63    82  120-122                                                                              NMR:                                                                              1.28 (3H, d, J=6.9), 3.02 (6H, s), 3.52 (1H, m),                              4.10 (1H, t, J=9.0), 4.70 (1H, t, J=9.0), 6.44 (1H,                           brs), 6.70-7.46 (7H, m).                                 64    94  80-82  NMR:                                                                              1.29 (3H, d, J=6.9), 3.19 (3H, s), 3.32-3.72 (1H,                             m),                                                                           3.76 (3H, s), 4.09 (1H, t, J=9.0), 4.70 (1H, t,                               J=9.0),                                                                       6.68-7.52 (7H, m), 7.73 (1H, brs).                       65    95  liquid IR: 3325 (ν.sub.NH), 1645 (ν.sub.c=o).                                  NMR:                                                                              0.92 (3H, t, J=7.2), 1.66 (2H, q, J=7.2), 3.00 (6H,                           s),                                                                           3.32 (1H, m), 4.21 (1H, dd, J=7.2, 9.0), 4.63 (1H,                            t,                                                                            J=9.0), 6.36 (1H, brs), 6.60-7.40 (7H, m).               66    85  liquid IR: 3325 (ν.sub.NH), 1675 (ν.sub.c=o).                                  NMR:                                                                              0.96 (3H, t, J=7.2), 1.68 (2H, q, J=7.2), 3.20 (3H,                           s),                                                                           3.26 (1H, m), 3.78 (3H, s), 4.21 (1H, dd, J=7.2,                              9.0),                                                                         4.65 (1H, t, J=9.0), 6.68-7.32 (7H, m), 7.63 (1H,                             brs).                                                    67    not less                                                                          liquid IR: 3320 (ν.sub.NH), 1645 (ν.sub.c=o).                       than 97    NMR:                                                                              0.94 (3H, t, J=7.2), 1.24-1.76 (4H, m), 3.00 (6H,                             s),                                                                           3.06 (1H, m), 4.20 (1H, dd, J=7.2, 9.0), 4.64 (1H,                            t,                                                                            J=9.0), 6.40 (1H, brs), 6.64-7.40 (7H, m).               68    92  liquid IR: 3325 (ν.sub.NH), 1675 (ν.sub.c=o).                                  NMR:                                                                              0.94 (3H, t, J=7.2), 1.28-1.80 (4H, m), 3.18 (3H,                             s),                                                                           3.20 (1H, m), 3.76 (3H, s), 4.20 (1H, dd, J=7.2,                              9.0),                                                                         4.65 (1H, d, J=9.0), 6.64-7.50 (7H, m), 7.63 (1H,                             brs).                                                    69    not less                                                                          liquid NMR:                                                                              0.82 (3H, d, J=6.4), 0.90 (3H, d, J=6.4), 1.70-2.10            than 97        (1H, m), 2.70 (3H, d, J=3.9), 3.12-3.40 (1H, m),                              4.20-4.66 (2H, m), 6.00 (1H, brs), 6.60-7.30 (7H,                             m),                                                                           7.92 (1H, brs).                                          70    92  124-125                                                                              NMR:                                                                              0.86 (3H, d, J=6.4), 0.94 (3H, d, J=6.4), 1.74-2.08                           (1H, m), 3.00 (6H, s), 3.16-3.42 (1H, m), 4.30-4.68                           (2H, m), 6.48 (1H, brs), 6.66-7.40 (7H, m).              71    not less                                                                          liquid NMR:                                                                              0.84 (3H, d, J=6.4), 0.92 (3H, d, J=6.4), 1.74-2.10            than 97        (1H, m), 3.16 (3H, s), 3.12-3.42 (1H, m), 4.30-4.66                           (2H, m), 6.68-7.50 (7H, m), 7.72 (1H, brs).              72    69  196-198                                                                              IR: 3325 (ν.sub.NH), 1639 (ν.sub.c=o).                 73    88  146-148                                                                              NMR:                                                                              0.98 (3H, d, J=6.4), 1.00 (3H, d, J=6.4), 1.40-2.06                           (3H, m), 2.65-3.32 (2H, m), 3.04 (6H, s), 4.72-4.96                           (1H, m), 6.24 (1H, brs), 6.60-7.36 (7H, m).              74    65  112-114                                                                              NMR:                                                                              0.98 (3H, d, J=6.4), 1.02 (3H, d, J=6.4), 1.48-2.00                           (3H, m), 2.66-3.32 (2H, m), 3.20 (3H, s), 3.80                                (3H, s), 4.72-5.00 (1H, m), 6.70-7.50 (7H, m),                                7.62 (1H, brs).                                          75    87  liquid NMR:                                                                              0.95 (3H, t, J=7.2), 1.20-1.86 (2H, m), 2.70 (3H,                             d,                                                                            J=4.5), 2.90-3.20 (1H, m), 3.52 (3H, s), 5.26 (1H,                            d,                                                                            J=2.7), 5.96 (1H, brs), 6.60-7.32 (7H, m), 7.91                               (1H,                                                                          brs).                                                    76    90  liquid NMR:                                                                              0.96 (3H, t, J=7.2), 1.30-1.90 (2H, m), 2.90-3.20                             (1H, m), 2.98 (6H, s), 3.53 (3H, s), 5.26 (1H, d,                             J=                                                                            2.7), 6.63 (1H, brs), 6.70-7.40 (7H, m).                 77    92  liquid NMR:                                                                              0.96 (3H, t, J=7.2), 1.30-1.90 (2H, m), 2.90-3.20                             (1H, m), 3.17 (3H, s), 3.52 (3H, s), 3.73 (3H, s),                            5.26 (1H, d, J=2.7), 6.68-7.52 (7H, m), 7.73 (1H,                             brs).                                                    78    80  149-151                                                                              IR: 3290, 3275 (ν.sub.NH), 1643 (ν.sub.c=o).           79    not less                                                                          104-106                                                                              IR: 3270 (ν.sub.NH), 1652 (ν.sub.c=o).                       than 97                                                                 80    90  145-146                                                                              IR: 3305 (ν.sub.NH), 1632 (ν.sub.c=o).                 81    80  131-133                                                                              IR: 3315 (ν.sub.NH), 1642 (ν.sub.c=o).                 82    not less                                                                          82-85  IR: 3340 (ν.sub.NH), 1664 (ν.sub.c=o).                       than 97                                                                 83    80  152-153                                                                              IR: 3280 (ν.sub.NH), 1636 (ν.sub.c=o).                 84    not less                                                                          liquid IR: 3320 (ν.sub.NH), 1675 (ν.sub.c=o).                       than 97                                                                 85    92  154-155                                                                              IR: 3340 (ν.sub.NH), 1640 (ν.sub.c=o).                 86    not less                                                                            95-96.5                                                                            IR: 3370 (ν.sub.NH), 1675 (ν.sub.c=o).                       than 97                                                                 87    not less                                                                          191.5-193                                                                            IR: 3350 (ν.sub.NH), 3290 (ν.sub.NH), 1636                                  (ν.sub.c=o).                                                than 97                                                                 88    75  115-116                                                                              IR: 3260 (ν.sub.NH), 1635 (ν.sub.c=o).                 89    83  99.5-101                                                                             IR: 3360 (ν.sub.NH), 1664 (ν.sub.c=o).                 90    95  97-99  IR: 3290 (ν.sub.NH), 1640 (ν.sub.c=o).                 91    not less                                                                          liquid NMR:                                                                              1.24 (3H, t, J=6.4), 1.26 (3H, d, J=6.4), 3.18 (3H,                           s),                                                            than 97        3.50-4.25 (3H, m), 3.74 (3H, s), 5.32 (1H, d,                                 J=2.6),                                                                       6.70-6.90 (3H, m), 6.90 (2H, d, J=9.0), 7.39 (2H,                             d,                                                                            J=9.0), 7.70 (1H, brs).                                  92    81  175-178                                                                              NMR:                                                                              1.27 (3H, s), 1.29 (3H, s), 3.05 (6H, s), 3.56 (3H,                           s), 5.14 (1H, s), 6.34 (1H, brs), 6.70-6.93 (3H,                              m),                                                                           7.85-8.08 (3H, m).                                       93    82  liquid NMR:                                                                              1.27 (3H, s), 1.29 (3H, s), 3.20 (3H, s), 3.65 (3H,                           s), 3.79 (3H, s), 5.14 (1H, s), 6.70-7.00 (4H, m),                            7.62 (1H, brs), 8.02 (1H, dd, J=2.7, 9.0), 8.13                               (1H,                                                                          d, J=2.7).                                               94    not less                                                                          156-157                                                                   than 97                                                                 95    81  52-54  NMR:                                                                              1.25 (3H, s), 1.28 (3H, s), 3.04 (6H, s), 3.55 (3H,                           s), 5.12 (1H, s), 6.34 (1H, brs), 6.70-7.04 (3H,                              m),                                                                           6.91 (2H, d, J=9.0), 7.32 (2H, d, J=9.0).                96    not less                                                                          liquid NMR:                                                                              1.25 (3H, s), 1.28 (3H, s), 3.19 (3H, s), 3.55 (3H,            than 97        s), 3.77 (3H, s), 6.70-7.04 (3H, m), 6.94 (2H, d,                             J=                                                                            9.0), 7.42 (2H, d, J=9.0), 7.68 (1H, brs).               97    63  165-168                                                                              NMR:                                                                              1.24 (3H, s), 1.28 (3H, s), 3.02 (6H, s), 3.54 (3H,                           s), 5.10 (1H, s), 6.32 (1H, brs), 6.74 (3H, brs),                             6.82 (1H, d, J=9.0), 7.18 (1H, dd, J=2.7, 9.0),                               7.55 (1H, d, J=2.7).                                     98    69  96-99  NMR:                                                                              1.25 (3H, s), 1.28 (3H, s), 3.19 (3H, s), 3.54 (3H,                           s), 3.76 (3H, s), 5.11 (1H, s), 6.75 (3H, brs),                               6.85 (1H, d, J=9.0), 7.34 (1H, dd, J=2.7, 9.0),                               7.63 (1H, d, J=2.7).                                     99    92  149-150                                                                              NMR:                                                                              0.60-1.06 (6H, m), 1.40-1.90 (2H, m), 2.78 (3H, s),                           3.56 (3H, s), 5.15 (1H, s), 6.64-7.36 (8H, m).           100   70  122-124                                                                              NMR:                                                                              0.64-1.04 (6H, m), 1.44-1.86 (2H, m), 3.05 (6H, s),                           3.55 (3H, s), 5.14 (1H, s), 6.24 (1H, brs),                                   6.68-7.40 (7H, m).                                       101   not less                                                                          97-98  NMR:                                                                              0.60-1.10 (6H, m), 1.44-1.92 (2H, m), 3.17 (3H, s),            than 97        3.54 (3H, s), 3.73 (3H, s), 5.13 (1H, s), 6.76 (3H,                           m), 6.90 (2H, d, J=9.0), 7.40 (2H, d, J=9.0), 7.76                            (1H, brs).                                               102   93  145.5-147                                                                            NMR:                                                                              0.77 (3H, t, J=7.5), 0.90 (3H, t, J=7.5), 1.44-1.92                           (4H, m), 2.76 (3H, s), 3.56 (3H, s), 5.14 (1H, s),                            6.68-7.36 (9H, m).                                       103   93  117-118                                                             104   89  liquid NMR:                                                                              0.78 (3H, t, J=7.1), 0.92 (3H, t, J=7.1), 1.42-1.96                           (4H, m), 3.18 (3H, s), 3.56 (3H, s), 3.76 (3H, s),                            5.14 (1H, s), 6.78 (3H, m), 6.90 (2H, d, J=9.0),                              7.40 (2H, d, J=9.0), 7.68 (1H, brs).                     105   not less                                                                          liquid NMR:                                                                              0.88 (3H, d, J=6.4), 0.92 (3H, d, J=6.4), 1.72-2.08            than 97        (1H, m), 2.99 (6H, s), 3.52 (3H, s), 5.32 (1H, d,                             J=                                                                            2.1), 6.55 (1H, brs), 6.70-7.40 (7H, m).                 106   not less                                                                          93-94  NMR:                                                                              0.90 (3H, d, J=6.4), 0.93 (3H, d, J=6.4), 1.80-2.08            than 97        (1H, m), 2.96-3.16 (1H, m), 3.19 (3H, s), 3.54 (3H,                           s), 3.76 (3H, s), 5.32 (1H, d, J=2.1), 6.70-7.50                              (7H, m), 7.64 (1H, brs).                                 107   not less                                                                          liquid IR: 3325 (ν.sub.NH), 1640 (ν.sub.c=o).                       than 97    NMR:                                                                              0.96 (3H, t, J=7.7), 1.23 (3H, t, J=7.1), 1.40-1.84                           (2H, m), 3.00 (6H, s), 3.01-3.16 (1H, m), 3.52-4.00                           (2H, m), 5.38 (1H, d, J=2.1), 6.47 (1H, brs),                                 6.70-7.44 (7H, m).                                       108   not less                                                                          liquid IR: 3325 (ν.sub.NH), 1675 (ν.sub.c=o).                       than 97    NMR:                                                                              0.97 (3H, t, J=7.2), 1.25 (3H, t, J=7.2), 1.63 (2H,                           q,                                                                            J=7.2), 3.13 (1H, m), 3.18 (3H, s), 3.76 (3H, s),                             3.50-4.16 (2H, m), 5.38 (1H, d, J=2.7), 6.68-6.90                             (3H, m), 6.90 (2H, d, J=9.0), 7.39 (2H, d, J=9.0),                            7.69 (1H, brs).                                          109   86  liquid NMR:                                                                              0.92 (3H, d, J=6.4), 0.96 (3H, d, J=6.4), 1.26 (3H,                           t,                                                                            J=6.4), 1.72-2.16 (1H, m), 2.78 (3H, d, J=5.1),                               3.04                                                                          (1H, dd, J=1.5, 5.1), 3.54-4.12 (2H, m), 5.28 (1H,                            d,                                                                            J=5.1), 5.44 (1H, d, J=1.5), 6.70-7.50 (8H, m).          110   72  liquid NMR:                                                                              0.88 (3H, d, J=6.4), 0.92 (3H, d, J=6.4), 1.24 (3H,                           t,                                                                            J=7.1), 1.80-2.12 (1H, m), 3.00 (6H, s), 3.02-3.12                            (1H, m), 3.52-4.06 (2H, m), 5.44 (1H, d, J=1.5),                              6.40 (1H, brs), 6.72-7.40 (7H, m).                       111   80  liquid NMR:                                                                              0.90 (3H, d, J=6.4), 0.92 (3H, d, J=6.4), 1.26 (3H,                           t,                                                                            J=7.1), 1.68-2.10 (1H, m), 3.04 (1H, m), 3.20 (3H,                            s), 3.50-4.08 (2H, m), 3.77 (3H, s), 5.44 (1H, d,                             J=                                                                            1.5), 6.72-7.04 (5H, m), 7.40 (2H, d, J=9.0), 7.65                            (1H, brs).                                               112   73    149-151.5                                                                          IR: 3285 (ν.sub.NH), 1643 (ν.sub.c=o).                 113   95  62-65  IR: 3310 (ν.sub.NH), 1660 (ν.sub.c=o).                 114   72  133-134                                                                              IR: 3280 (ν.sub.NH), 1638 (ν.sub.c=o).                 115   not less                                                                          77-79  IR: 3310 (ν.sub.NH), 1659 (ν.sub.c=o).                       than 97                                                                 116   80  145-147                                                                              IR: 3355 (ν.sub.NH), 3305 (ν.sub.NH), 1650                                  (ν.sub.c=o).                                          117   77  157-158                                                                              NMR:                                                                              1.30-2.16 (8H, m), 3.12 (6H, s), 3.13-3.36 (1H, m),                           4.64-4.88 (1H, m), 6.32 (1H, brs), 6.76-7.48 (7H,                             m).                                                      118   73  118-120                                                                              NMR:                                                                              1.20-2.10 (8H, m), 3.00-3.30 (1H, m), 3.20 (3H, s),                           3.78 (3H, s), 4.52-4.80 (1H, m), 6.68-7.52 (7H, m),                           7.63 (1H, brs).                                          119   73  137.5-139                                                                            IR: 3325 (ν.sub.NH), 1645 (ν.sub.c=o).                 120   79  164- 165                                                                             NMR:                                                                              1.00-2.10 (10H, m), 3.05 (6H, s), 3.40-3.62 (1H,                              m),                                                                           4.30-4.60 (1H, m), 6.25 (1H, brs), 6.64-7.44 (7H,                             m).                                                      121   not less                                                                          127-128                                                                              NMR:                                                                              0.96-2.10 (10H, m), 3.19 (3H, s), 3.30-3.60 (1H,                              m),                                                            than 97        3.76 (3H, s), 4.00-4.56 (1H, m), 6.70-7.52 (7H, m),                           7.68 (1H, brs).                                          122   92  57-59  NMR:                                                                              0.80-2.10 (10H, m), 2.76 (3H, d, J=3.9), 3.36-3.70                            (1H, m), 4.48-4.96 (1H, m), 5.66 (1H, d, J=2.9),                              6.50-7.34 (7H, m), 7.52 (1H, s).                         123   79  56-58  IR: 3325 (ν.sub.NH), 1650 (ν.sub.c=o).                 124   60  liquid NMR:                                                                              0.80-2.10 (10H, m), 3.20 (3H, s), 3.40-3.70 (1H,                              m),                                                                           3.78 (3H, s), 4.48-4.96 (1H, m), 6.68-7.52 (7H, m),                           7.70 (1H, brs).                                          125   90  176-178                                                             126   84  138.5-140                                                                            NMR:                                                                              3.02 (6H, s), 5.95 (2H, s), 6.43 (1H, dd, J=2.7,                              9.0),                                                                         6.45 (1H, brs), 6.57 (1H, d, J=2.7), 6.74 (1H, d,                             J=                                                                            9.0), 6.90 (2H, d, J=9.0), 7.32 (1H, d, J=9.0).          127   not less                                                                          90-91  NMR:                                                                              3.09 (3H, s), 3.77 (3H, s), 5.96 (2H, s), 6.36 (1H,            than 97        dd, J=2.7, 9.0), 6.57 (1H, d, J=2.7), 6.76 (1H, d,                            J=                                                                            9.0), 6.84 (2H, d, J=9.0), 7.42 (2H, d, J=9.0),                               7.64 (1H, brs).                                          128   89  150-151                                                             129   81  125-126                                                                              NMR:                                                                              1.01 (3H, t, J=7.2), 1.61 (3H, s), 1.95 (2H, q,                               J=7.2),                                                                       3.02 (6H, s), 6.38 (1H, dd, J=2.7, 8.1), 6.47 (1H,                            d,                                                                            J=2.7), 6.64 (1H, d, J=8.1), 6.90 (2H, d, J=9.0),                             7.30 (2H, d, J=9.0).                                     130   88  99.5-101                                                                             NMR:                                                                              1.02 (3H, t, J=7.2), 1.62 (3H, s), 1.95 (2H, q,                               J=7.2),                                                                       3.18 (3H, s), 3.76 (3H, s), 6.38 (1H, dd, J=2.7,                              8.1),                                                                         6.47 (1H, d, J=2.7), 6.63 (1H, d, J=8.1), 6.93 (2H,                           d,                                                                            J=9.0), 7.39 (2H, d, J=9.0), 7.65 (1H, brs).             131   56  169-170                                                                              IR: 3285 (ν.sub.NH), 1642 (ν.sub.c=o).                 132   86  112-113                                                                              IR: 3330 (ν.sub.NH), 1665 (ν.sub.c=o).                 133   76  145-147                                                                              NMR:                                                                              1.67 (6H, s), 3.02 (6H, s), 6.20-6.80 (3H, m),                                6.89 (2H,d,J=9.0), 7.29 (2H, d, J=(2H, d,                                     J=-   IR: 3295 (ν.sub.NH), 1637 (ν.sub.c=o).       134   90  93-94  IR: 3350 (ν.sub.NH), 1662 (ν.sub.c=o).                 135   72  103.5-104.5                                                         136   not less                                                                          141-143                                                                              NMR:                                                                              1.80 (3H, s), 3.03 (6H, s), 3.33 (3H, s), 6.45 (1H,            than 97        dd, J=2.7, 7.2), 6.56 (1H, d, J=2.7), 6.72 (1H, d,                            J=7.2), 6.73 (2H, d, J=9.0), 7.31 (2H, d, J=9.0).        137   94  117-118                                                                              NMR:                                                                              1.81 (3H, s), 3.20 (3H, s), 3.74 (3H, s), 3.78 (3H,                           s), 6.46 (1H, dd, J=2.7, 7.2), 6.56 (1H, d, J=2.7),                           6.75 (1H, d, J=7.2), 6.93 (2H, d, J=9.0), 7.42 (2H,                           d,                                                                            J=9.0), 7.67 (1H, brs).                                  138   not less                                                                          119-120                                                                              IR: 3300 (ν.sub.NH), 1640 (ν.sub.c=o).                       than 97                                                                 139   not less                                                                          liquid IR: 3320 (ν.sub.NH), 1675 (ν.sub.c=o).                       than 97                                                                 140   92  liquid NMR:                                                                              1.02 (3H, t, J=7.2), 1.21 (3H, t, J=7.2), 2.06 (2H,                           q,                                                                            J=7.2), 3.03 (6H, s), 3.61 (2H, q, J=7.2),                                    6.20-6.80                                                                     (3H, m), 6.91 (2H, d, J=9.0), 7.30 (3H, d, J=9.0).       141   not less                                                                          liquid NMR:                                                                              1.21 (3H, t, J=7.2), 1.27 (3H, t, J=7.2), 2.07 (2H,                           q,                                                             than 97        J=7.2), 3.19 (3H, s), 3.62 (2H, q, J=7.2), 3.77                               (3H,                                                                          s), 6.32-6.88 (3H, m), 6.93 (2H, d, J=9.0), 7.40                              (2H,                                                                          d, J=9.0), 7.66 (1H, brs).                               142   83  103-104                                                                              IR: 3300 (ν.sub.NH), 1635 (ν.sub.c=o).                 143   not less                                                                          liquid IR: 3390 (ν.sub.NH), 3300 (ν.sub.NH), 1668                                  (ν.sub.c=o).                                                than 97                                                                 144   80  113-114                                                                              IR: 3275 (ν.sub.NH), 1633 (ν.sub.c=o).                 145   not less                                                                          liquid IR: 3390 (ν.sub.NH), 3300 (ν.sub.NH), 1668                                  (ν.sub.c=o).                                                than 97                                                                 146   83    165-166.5                                                                          IR: 3300 (ν.sub.NH), 1627 (ν.sub.c=o).                 147   85  129.5-131                                                                            IR: 3290 (ν.sub.NH), 1635 (ν.sub.c=o).                 148   87  105-106                                                                              IR: 3350 (ν.sub.NH), 1668 (ν.sub.c=o).                 149   81  151-152                                                                              IR: 3300 (ν.sub.NH), 1627 (ν.sub.c=o).                 150   70  112.5- 114                                                                           IR: 3290 (ν.sub.NH), 1634 (ν.sub.c=o).                 151   86  liquid IR: 3350 (ν.sub.NH), 1665 (ν.sub.c=o).                 152   88  164.5-168                                                                            IR: 3400 (ν.sub.NH), 3290 (ν.sub.NH), 1650                                  (ν.sub.c=o).                                          153   85    192-193.5                                                                          IR: 3290 (ν.sub.NH), 1637 (ν.sub.c=o).                 154   81  131.5-134                                                                            IR: 3325 (ν.sub.NH), 1662 (ν.sub.c=o).                 155   71    176-177.5                                                                          IR: 3340 (ν.sub. NH), 1635 (ν.sub.c=o).                156   not less                                                                          109-110                                                                              IR: 3290 (ν.sub.NH), 1657 (ν.sub.c=o).                       than 95                                                                 157   78  162.5-164                                                                            IR: 3250 (ν.sub.NH), 1635 (ν.sub.c=o).                 158   85  102-104                                                                              IR: 3280 (ν.sub.NH), 1660 (ν.sub.c=o).                 159   76    162-168.5                                                                          IR: 3330 (ν.sub.NH), 1644 (ν.sub.c=o).                 160   92  117-118                                                                              IR: 3330 (ν.sub.NH), 1665 (ν.sub.c=o).                 161   84  119-122                                                                              NMR:                                                                              1.38 (3H, d, J=7.2), 160-2.00 (2H, m), 2.64-2.94                              (2H, m), 3.02 (6H, s), 4.00-4.28 (1H, m), 6.40-7.20                           (3H, m), 6.85 (1H, d, J=9.0), 7.95 (1H, dd, J=2.7,                            9.0), 8.05 (1H, d, J=2.7).                               162   not less                                                                          liquid NMR:                                                                              1.38 (3H, d, J=7.2), 1.60-2.00 (2H, m), 2.64-3.00              than 97        (2H, m), 3.20 (3H, s), 3.79 (3H, s), 4.00-4.16 (1H,                           m), 6.48-7.20 (3H, m), 6.89 (1H, d, J=9.0), 7.71                              (1H,                                                                          brs), 8.05 (1H, dd, J=2.7, 9.0), 8.16 (1H, d,                                 J=2.7).                                                  163   71  125.5-126.5                                                         164   86  114-116                                                                              IR: 3315 (ν.sub.NH), 1640 (ν.sub.c=o).                 165   not less                                                                          liquid IR: 3325 (ν.sub.NH), 1680 (ν.sub.c=o).                       than 97                                                                 166   90  148.5-149.5                                                                          IR: 3355 (ν.sub.NH), 1646 (ν.sub.c=o).                 167   96  118-119                                                                              IR: 3350 (ν.sub.NH), 1662 (ν.sub.c=o).                 168   not less                                                                          146-148                                                                   than 97                                                                 169   82  129-131                                                                              NMR:                                                                              1.32 (6H, s), 17.78 (2H, t, J=7.2), 2.72 (2H, t,                              J=7.2),                                                                       3.02 (6H, s), 6.33 (1H, brs), 6.39 (1H, d, J=2.7),                            6.47 (1H, d, J=9.0), 6.97 (1H, d, J=7.2), 6.96 (2H,                           d,                                                                            J=9.0), 7.34 (2.H, d, J=9.0).                            170   91  98-99  NMR:                                                                              1.32 (6H, s), 1.80 (2H, t, J=7.2), 2.75 (2H, t,                               J=7.2),                                                                       3.19 (3H, s), 3.76 (3H, s), 6.52 (1H, d, J=2.7),                              6.58 (1H, dd, J=2.7, 7.2), 6.86 (1H, d, J=9.0),                               7.04 (1H, d, J=7.2), 7.68 (1H, brs), 8.01 (1H, dd,                            J=2.7, 9.0), 8.14 (1H, d, J=2.7).                        171   92  131-132                                                             173   77  104-106                                                                              NMR:                                                                              1.32 (6H, s), 1.76 (2H, t, J=7.2), 2.73 (2H, t,                               J=9.0),                                                                       3.19 (3H, s), 3.77 (3H, s), 6.39 (1H, d, J=2.7),                              6.49 (1H, dd, J=2.7, 9.0), 6.98 (3H, d, J=9.0),                               7.42 (2H, d, J=9.0), 7.68 (1H, brs).                     174   73  159-161                                                                              IR: 3275 (ν.sub.NH), 1635 (ν.sub.c=o).                 175   70  95-97  NMR:                                                                              1.32 (6H, s), 1.78 (2H, t, J=7.2), 2.71 (2H, t,                               J=7.2),                                                                       3.20 (3H, s), 3.78 (3H, s), 6.32 (1H, d, J=2.7),                              6.45                                                                          (1H, dd, J=2.7, 9.0), 7.01 (2H, d, J=9.0), 7.32                               (1H,                                                                          dd, J=2.7, 9.0), 7.67 (1H, d, J=2.7), 7.72 (1H,                               brs).                                                    176   78  133-134                                                                              IR: 3300 (ν.sub.NH), 1656 (ν.sub.c=o), 1530                                 (ν.sub.NO.sbsb.2), 1370 (ν.sub.NO.sbsb.2).         177   not less                                                                          liquid IR: 3360 (ν.sub.NH), 1660 (ν.sub.c=o), 1540                                 (ν.sub.NO.sub.2), 1365 (ν.sub.NO.sub.2).                 than 97                                                                 178   96  119-121                                                                              IR: 3300 (ν.sub.NH), 1640 (ν.sub.c=o).                 179   not less                                                                          liquid IR: 3320 (ν.sub.NH), 1675 (ν.sub.c=o).                       than 97                                                                 180   76  69-70  NMR:                                                                              1.29 (3H, s), 1.33 (3H, s), 1.36 (3H, d, J=6.3),                              1.62                                                                          (1H, s), 1.69 (1H, s), 3.00 (6H, s), 3.06 (1H,                                brs),                                                                         4.20 (1H, q, J=6.3), 6.44-6.72 (2H, m), 6.82 (1H,                             d,                                                                            J=9.0), 7.21 (1H, d, J=9.0), 7.90 (1H, dd, J=2.7,                             9.0), 8.02 (1H, d, J=2.7).                               181   95  43-45  NMR:                                                                              1.28 (3H, s), 1.30 (3H, s), 1.35 (3H, d, J=6.3),                              1.62                                                                          (1H, s), 1.69 (1H, s), 3.18 (3H, s), 3.75 (3H, s),                            6.51 (1H, d, J=2.7), 6.59 (1H, dd, J=2.7, 8.1),                               6.85 (1H, d, J=9.0), 7.22 (1H, d, J=8.1), 7.64 (1H,                           brs), 8.61 (1H, dd, J=2.7, 9.0), 8.13 (1H, d,                                 J=2.7).                                                  182   89  164-165                                                                              IR: 3365 (ν.sub.NH), 1645 (ν.sub.c=o).                 183   91  126-127                                                                              IR: 3330 (ν.sub.NH), 1666 (ν.sub.c=o).                 184   88    125-126.5                                                                          IR: 3350 (ν.sub.NH), 1682 (ν.sub.c=o).                 185   not less                                                                          133-134                                                                              IR: 3335 (ν.sub.NH), 1638 (ν.sub.c=o).                       than 97                                                                 186   not less                                                                          122-123                                                                              IR: 3320 (ν.sub.NH), 1660 (ν.sub.c=o).                       than 97                                                                 187   69  129-130                                                                              NMR:                                                                              1.32 (3H, s), 1.41 (3H, s), 1.99 (1H, d, J=7.2),                              2.03 (1H, d, J=7.2), 3.04 (6H, s), 3.46 (3H, s),                              4.39 (1H, t, J=7.2), 6.29 (1H, brs),                                          6.37 (1H, d, J=2.7), 6.51 (1H, dd, J=2.7, 9.0),                               6.97 (2H, d, J=9.0), 7.30 (1H, d, J=9.0),                                     7.34 (2H, d, J=9.0).                                     188   92  96.5-97.5                                                                            NMR:                                                                              1.33 (3H, s), 1.42 (3H, s), 1.99 (1, H, d, J=7.2),                            2.04 (1H, d, J=7.2), 3.19 (3H, s), 3.46 (3H, s),                              3.77 (3H, s), 6.37 (1H, d, J=2.7), 6.55 (1H, dd,                              J=2.7,                                                                        9.0), 6.99 (2H, d, J=9.0), 7.31 (1H, d, J=9.0),                               7.42 (2H, d, J=9.0), 7.67 (1H, brs).                     189   not less                                                                          179-182                                                                              IR: 3320 (ν.sub.NH), 1638 (ν.sub.c=o).                       than 97                                                                 190   not less                                                                          97-98                                                                     than 97                                                                 191   not less                                                                          70-71                                                                     than 97                                                                 192   not less                                                                          189-200                                                                   than 97                                                                 193   67  143-145                                                                              NMR:                                                                              1.26 (3H, s), 1.41 (3H, s), 1.49 (3H, s),                                     1.81 (1H, d, J=14.0), 2.03 (1H, d, J=14.0),                                   3.02 (6H, s), 3.21 (3H, s), 6.29 (1H, brs),                                   6.43 (1H, d, J=2.7), 6.59 (1H, dd, J=2.7, 9.0),                               6.98 (2H, d, J=9.0), 7.21 (1H, d, J=9.0),                                     7.35 (2H, d, J=9.0).                                     194   not less                                                                          92-93  NMR:                                                                              1.26 (3H, s), 1.42 (3H, s), 1.58 (3H, s),                      than 97        1.84 (1H, d, J=13.5), 2.05 (1H, d, J=13.5),                                   3.20 (3H, s), 3.22 (3H, s), 6.45 (1H, d, J=2.7),                              6.59 (1H, dd, J=2.7, 9.0), 7.00 (2H, d, J=9.0),                               7.20 (1H, d, J=9.0), 7.43 (2H, d, J=9.0),                                     7.70 (1H, brs).                                          195   not less                                                                          211-212                                                                   than 97                                                                 196   70  164-165                                                             197   80    92-93.5                                                           198   72  210-212                                                                              IR: 3350 (ν.sub.NH), 3280 (ν.sub.NH), 1644                                  (ν.sub.c=o),                                                               1520 (ν.sub.NO.sbsb.2), 1346 (ν.sub.NO.sbsb.2).    199   63  163-164                                                                              IR: 3410 (ν.sub.NH), 3320 (ν.sub.NH), 1646                                  (ν.sub.c=o),                                                               1524 (ν.sub.NO.sbsb.2), 1350 (ν.sub.NO.sbsb.2).    200   86  142-144                                                                              IR: 3260 (ν.sub.NH), 1650 (ν.sub.c=o),                                      1525 (ν.sub.NO.sbsb.2), 1340 (ν.sub.NO.sbsb.2).    201   not less                                                                          201-202                                                                   than 97                                                                 202   not less                                                                          174-175                                                                   than 97                                                                 203   not less                                                                          145-174                                                                   than 97                                                                 204   69  186-188                                                                              NMR:                                                                              1.00 (3H, t, J=7.2), 1.45 (3H, s), 1.50 (3H, s),                              1.80 (1H, d, J=14.0), 2.04 (1H, d, J=14.0),                                   3.03 (6H, s), 3.55 (2H, q, J=7.2), 6.30 (1H, brs),                            6.43 (1H, d, J=2.7), 6.58 (1H, dd, J=2.7, 9.0),                               6.98 (2H, d, J=9.0), 7.21 (1H, d, J=9.0),                                     7.34 (2H, d, J=9.0).                                     205   not less                                                                          liquid IR: 3325 (ν.sub.NH), 1675 (ν.sub.c=o).                       than 97                                                                 206   82  153.5-154.5                                                         207   not less                                                                          liquid NMR:                                                                              0.72 (3H, t, J=7.2), 1.20-1.60 (2H, m), 1.28 (3H,                             s),                                                            than 97        1.46 (3H, s), 1.52 (3H, s), 1.82 (1H, d, J=13.5),                             206 (1H, d, J=13.5), 3.20 (3H, s), 3.47 (3H, t,                               J=7.2),                                                                       3.69 (3H, s), 6.44 (1H, d, J=2.7), 6.60 (1H, dd, J=                           2.7, 9.0), 6.99 (2H, d, J=9.0), 7.23 (1H, d,                                  J=9.0),                                                                       7.43 (2H, d, J=9.0), 7.67 (1H, brs).                     208   not less                                                                          173-174                                                                   than 97                                                                 209   81  62-63  IR: 3320 (ν.sub.NH), 1653 (ν.sub.c=o).                 210   not less                                                                          liquid IR: 3320 (ν.sub.NH), 1673 (ν.sub.c=o).                       than 97                                                                 211   61  liquid NMR:                                                                              1.82-2.20 (2H, m), 3.00 (6H, s), 3.43 (3H, s),                                4.10-4.36 (3H, m), 6.34-6.60 (3H, m),                                         6.82-7.40 (5H, m).                                       212   69  liquid NMR:                                                                              1.88-2.20 (2H, m), 3.18 (3H, s), 3.42 (3H, s),                                3.74 (3H, s), 4.06-4.34 (3H, m), 6.40-6.60 (2H, m),                           6.86-7.50 (5H, m), 7.76 (1H, brs).                       213   58  143-145                                                             214   not less                                                                          liquid NMR:                                                                              1.00 (3H, t, J=7.2), 1.40-2.16 (4H, m), 2.50-3.00              than 97        (2H, m), 3.18 (3H, s), 3.70-4.04 (1H, m),                                     3.76 (3H, s), 6.32-7.56 (7H, m), 7.67 (1H, brs).         215   80  146-148                                                             216   90  151-153                                                             217   not less                                                                          112-114                                                                   than 97                                                                 218   85  liquid NMR:                                                                              1.90 (2H, m), 2.60 (2H, m), 2.62 (3H, d, J=5.4),                              3.36 (3H, s), 4.98 (1H, t, J=1.8), 5.90 (1H, brs),                            6.38 (2H, m), 6.80 (3H, d, J=9.0), 7.12 (2H, d,                               J=9.0),                                                                       7.84 (1H, brs).                                          219   76  123-125                                                             220   70  liquid NMR:                                                                              1.90 (2H, m), 2.56 (2H, m), 3.04 (3H, s),                                     3.40 (3H, s), 3.64 (3H, s), 5.01 (1H, t, J=1.8),                              6.30-6.96 (3H, m), 6.88 (2H, d, J=9.0),                                       7.36 (2H, d, J=9), 7.66 (1H, brs).                       221   84  139-140                                                             222   not less                                                                          88-90                                                                     than 97                                                                 223   89  136-138                                                             224   85  127-129                                                             225   87  liquid NMR:                                                                              1.00 (3H, t, J=7.2), 1.80 (4H, m), 2.60 (1H, m),                              3.21 (3H, s), 3.82 (3H, s), 4.16 (2H, t, J=5.4),                              6.42 (1H, d, J=2.7), 6.49 (1H, dd, J=2.7, 8.1),                               6.98 (2H, d, J=9.0), 7.06 (1H, d, J=8.1),                                     7.42 (2H, d, J=9.0), 7.64 (1H, brs).                     226   61  158-160                                                             227   88  139-142                                                             228   not less                                                                          liquid NMR:                                                                              0.96 (3H, d, J=7.2), 1.16 (3H, d, J=7.2),                      than 97        2.00-2.40 (1H, m), 2.70-3.10 (1H, m), 3.17 (3H, s),                           3.75 (3H, s), 3.80-4.10 (2H, m), 6.44 (1H, d,                                 J=2.7),                                                                       6.50 (1H, dd, J=2.7, 8.1), 6.98 (2H, d, J=8.1),                               7.04 (1H, d, J=8.1), 7.35 (2H, d, J=8.1),                                     7.70 (1H, brs).                                          229   not less                                                                          58.5-59.5                                                                 than 97                                                                 230   90  158-160                                                             231   90  157-158                                                             232   90  liquid NMR:                                                                              1.30, 1.35 (total 3H, d, J=7.2), 1.60-2.28 (2H, m),                           2.94 (1H, m), 2.98 (6H, s), 3.47, 3.51 (total 3H,                             s),                                                                           5.07 (1H, m), 6.36-7.44 (8H, m).                         233   92  liquid NMR:                                                                              1.30, 1.36 (total 3H, d, J=7.2), 1.60-2.30 (2H, m),                           3.00 (1H, m), 3.19 (3H, s), 3.47, 3.52 (total 3H,                             s),                                                                           3.77 (3H, m), 5.08 (1H, m), 6.40-7.56 (7H, m),                                7.68 (1H, brs).                                          234   90  liquid NMR:                                                                              1.00-1.50 (6H, m), 1.60-2.28 (2H, m), 3.02 (6H, s),                           3.08 (1H, m), 3.24-4.08 (2H, m), 5.18 (1H, dd,                                J=3.6,                                                                        7.2), 6.38 (1H, brs), 6.40-7.48 (7H, m).                 235   not less                                                                          liquid NMR:                                                                              1.02-1.58 (6H, m), 1.60-2.30 (2H, m), 3.10 (1H, m),            than 97        3.20 (3H, s), 3.50-4.20 (2H, m), 3.79 (3H, s),                                5.18 (1H, dd, J=3.6, 7.2), 6.40-7.56 (7H, m),                                 7.68 (1H, brs).                                          236   80  179-180                                                             237   not less                                                                          129-131                                                                              NMR:                                                                              1.40 (3H, d, J=7.2), 1.60-2.44 (2H, m), 3.18 (3H,                             s),                                                            than 97        3.44 (3H, s), 3.76 (3H, s), 4.20 (1H, m),                                     4.56 (1H, dd, J=6.3, 10.8), 6.36 (1H, d, J=2.7),                              6.55 (1H, dd, J=2.7, 9.0), 6.97 (2H, d, J=9.0),                               7.30 (1H, d, J=9.0), 7.42 (2H, d, J=9.0), 7.64 (1H,                           m).                                                      238   82  135-137                                                             239   not less                                                                          151-152                                                                   than 97                                                                 240   not less                                                                          109-110                                                                              NMR:                                                                              0.96 (3H, d, J=7.2), 1.26 (3H, d, J=7.2),                      than 97        2.00-3.08 (3H, m), 3.19 (3H, s), 3.77 (3H, s),                                4.08-4.20 (1H, m), 6.42 (1H, d, J=2.7), 6.47 (1H,                             dd,                                                                           J=2.7, 9.0), 6.96 (1H, d, J=9.0), 6.98 (2H, d,                                J=9.0),                                                                       7.42 (2H, d, J=9.0), 7.68 (1H, brs).                     241   71  liquid NMR:                                                                              0.8-1.12 (6H, m), 1.20-1.81 (3H, m),                                          2.20-2.80 (2H, m), 3.04 (6H, s), 3.98 (1H, m),                                6.30 (1H, brs), 6.40-7.40 (7H, m).                       242   not less                                                                          115-117                                                                   than 97                                                                 243   86  142-143                                                                              IR: 3335 (ν.sub.NH), 1644 (ν.sub.c=o).                 244   88  88-90  IR: 3360 (ν.sub.NH), 1660 (ν.sub.c=o).                 245   81  109-111                                                                              IR: 3290 (ν.sub.NH), 1638 (ν.sub.c=o).                 246   not less                                                                          liquid IR: 3320 (ν.sub.NH), 1675 (ν.sub.c=o).                       than 97    NMR:                                                                              0.92 (3H, t, J=7.2), 1.24 (3H, s), 1.40-1.92 (6H,                             m),                                                                           2.70 (2H, t, J= 7.2), 3.18 (3H, s), 3.76 (3H, s),                             6.40 (1H, d, J=2.7), 6.46 (1H, dd, J=2.7, 9.0),                               6.97 (3H, d, J=9.0), 7.40 (2H, d, J=9.0),                                     7.65 (1H, brs).                                          247   82  119.5-120                                                                            IR: 3350 (ν.sub.NH), 1641 (ν.sub.c=o).                 248   not less                                                                            79-80.5                                                                            IR: 3310 (ν.sub.NH), 1660 (ν.sub.c=o).                 249   87  132.5-134                                                                            IR: 3360 (ν.sub.NH), 1647 (ν.sub.c=o).                 250   not less                                                                          94-95  IR: 3360 (ν.sub.NH), 1662 (ν.sub.c=o).                       than 97                                                                 251   77  105-106                                                                              NMR:                                                                              0.89 (6H, t, J=7.0), 1.25-1.67 (6H, m), 1.77 (2H,                             t,                                                                            J=7.2), 2.68 (2H, t, J=7.2), 3.02 (6H, s),                                    6.26 (1H, brs), 6.39 (1H, d, J=2.7), 6.45 (1H, dd,                            J=2.7, 9.0), 6.93 (1H, d, J=9.0), 6.95 (2H, d,                                J=9.0),                                                                       7.39 (2H, d, J=9.0).                                     252   not less                                                                          liquid NMR:                                                                              0.89 (6H, t, J=7.5), 1.20-1.66 (6H, m), 1.77 (2H,                             t,                                                             than 97        J=7.2), 2.67 (2H, t, J=7.2), 3.17 (3H, s),                                    3.75 (3H, s), 6.39 (1H, d, J=2.7), 6.44 (1H, dd,                              J=2.7, 9.0), 6.95 (1H, d, J=9.0), 6.97 (2H, d,                                J=9.0),                                                                       7.40 (2H, d, J=9.0), 7.69 (1H, brs).                     253   not less                                                                          113-116                                                                              IR: 3330 (ν.sub.NH), 1637 (ν.sub.c=o).                       than 97                                                                 254   85    58-59.5                                                                            IR: 3355 (ν.sub.NH), 1638 (ν.sub.c=o).                 255   not less                                                                            99-100.5                                                                           IR: 3330 (ν.sub.NH), (ν.sub.c=o).                            than 97                                                                 256   not less                                                                            136-137.5                                                               than 97                                                                 257   not less                                                                            144-144.5                                                                          IR: 3310 (ν.sub.NH), 1648 (ν.sub.c=o).                       than 97    NMR:                                                                              1.49 (3H, s), 1.62-2.08 (2H, m), 2.36-2.92 (2H, m),                           3.03 (6H, s), 3.27 (3H, s), 6.40 (1H, brs),                                   6.44-7.46 (7H, m).                                       258   not less                                                                          liquid IR: 3330 (ν.sub.NH), 1672 (ν.sub. c=o).                      than 97    NMR:                                                                              1.52 (3H, s), 1.72-2.24 (2H, m), 2.40-3.04 (2H, m),                           3.20 (3H, s), 3.29 (3H, s), 3.77 (3H, s), 6.47 (1H,                           d),                                                                           J=2.7), 6.52 (1H, dd, J=2.7, 9.0), 7.00 (3H, d,                               J=9.0), 7.43 (2H, d, J=9.0), 7.66 (1H, brs).             259   77  159.5-160.5                                                                          IR: 3270 (ν.sub.NH), 1632 (ν.sub.c=o).                                  NMR:                                                                              1.05 (3H, t, J=7.2), 1.53 (3H, s), 1.70-2.24 (2H,                             m),                                                                           2.56-3.20 (2H, m), 3.03 (6H, s), 3.59 (2H, q,                                 J=7.2),                                                                       6.34 (1H, brs), 6.40-7.44 (7H, m).                       260   not less                                                                          liquid IR: 3310 (ν.sub.NH), 1670 (ν.sub.c=o).                       than 97                                                                 261   85  liquid NMR:                                                                              0.85 (3H, d, J=7.2), 1.12 (3H, d, J=7.2), 1.52 (3H,                           s),                                                                           1.64-2.24 (2H, m), 2.36-2.80 (2H, m), 3.00 (6H, s),                           4.22 (1H, m), 6.38-6.58 (3H, m), 6.84-7.06 (3H, m),                           7.22-7.40 (2H, m).                                       262   91  liquid NMR:                                                                              0.84 (3H, d, J=7.2), 1.13 (3H, d, J=7.2), 1.54 (3H,                           s),                                                                           1.64-2.18 (2H, m), 2.30-3.00 (2H, m), 3.15 (3H, s),                           3.73 (3H, s), 4.20 (1H, m), 6.36-6.58 (2H, m),                                6.84-7.04 (3H, m).                                       263   not less                                                                          147-148                                                                   than 97                                                                 264   90  141-143                                                                              IR: 3290 (ν.sub.NH), 1636 (ν.sub.c=o).                 265   not less                                                                          liquid IR: 3420 (ν.sub.NH), 3330 (ν.sub.NH), 1675                                  (ν.sub.c=o).                                                than 97    NMR:                                                                              0.96 (3H, t, J=7.2), 1.64-14 2.24 (4H, m),                                    2.40-3.00                                                                     (2H, m), 3.19 (3H, s), 3.23 (3H, s), 3.76 (3H, s),                            6.47 (1H, d, J=2.7), 7.32 (1H, dd, J=2.7, 9.0),                               6.98 (3H, d, J=9.0), 7.42 (2H, d, J=9.0),                                     7.67 (1H, brs).                                          266   not less                                                                          114-116                                                                   than 97                                                                 267   not less                                                                            146-147.5                                                               than 97                                                                 268   not less                                                                          liquid NMR:                                                                              1.29 (3H, t, J=7.2), 1.50 (3H, s), 1.90-2.20 (2H,                             m),                                                            than 97        3.08 (1H, m), 3.19 (3H, s), 3.26 (3H, s),                                     3.76 (3H, s), 6.44 (1H, d, J=2.7), 6.56 (1H, dd,                              J=2.7,                                                                        9.0), 6.98 (2H, d, J=9.0), 7.16 (1H, d, J=9.0),                               7.42 (2H, d, J=9.0), 7.68 (1H, brs).                     269   not less                                                                          163.5-164.5                                                               than 97                                                                 270   77  167-168                                                             271   84  liquid NMR:                                                                              0.95 (3H, t, J=7.2), 1.30 (3H, d, J=6.3), 1.60-2.24                           (4H, m), 3.00 (1H, m), 3.18 (3H, s), 3.22 (3H, s),                            3.76 (3H, s), 6.47 (1H, d, J=2.7), 6.55 (1H, dd, J=                           2.7, 9.0), 6.97 (2H, d, J=9.0), 7.17 (1H, d,                                  J=9.0),                                                                       7.42 (2H, d, J=9.0), 7.70 (1H, brs).                     272   90  liquid NMR:                                                                              1.07 (3H, d, J=7.2), 1.38 (3H, d, J=7.2), 1.60-2.00                           (1H, m), 3.02 (6H, s), 3.31 (3H, s), 3.80-4.36 (2H,                           m), 6.20-7.44 (8H, m).                                   273   87  liquid NMR:                                                                              1.06 (3H, d, J=7.2), 1.37 (3H, d, J=7.2), 1.64-                               2.10                                                                          (1H, m), 3.18 (3H, s), 3.30 (3H, s), 3.76 (3H, s),                            3.90-4.40 (2H, m), 6.38 (1H, d, J=2.7), 6.52 (1H,                             dd, J=2.7, 9.0), 6.98 (2H, d, J=9.0), 7.25 (1H, d,                            J=9.0), 7.43 (2H, d, J=9.0), 7.68 (1H, brs).             274   not less                                                                          163-164                                                                   than 97                                                                 275   92  58-59  NMR:                                                                              0.99 (3H, d, J=7.2), 1.13 (3H, s), 1.35 (3H, s),                              1.60-2.08 (1H, m), 2.30-2.88 (2H, m), 2.98 (6H, m),                           6.30-7.44 (8H, m).                                       276   not less                                                                          82.5-83.5                                                                            NMR:                                                                              1.01 (3H, d, J=7.2), 1.15 (3H, s), 1.36 (3H, s),               than 97        1.68-2.12 (1H, m), 2.19 (1H, dd, J=9.0, 16.2),                                2.64 (1H, d, J=6.3, 16.2), 3.19 (3H, s), 3.76 (3H,                            s),                                                                           6.39 (1H, d, J=2.7), 6.46 (1H, dd, J=2.7, 9.0),                               6.95 (1H, d, J=9.0), 6.98 (2H, d, J=9.0), 7.42 (2H,                           d,                                                                            J=9.0), 7.68 (1H, brs).                                  277   94     146-147.5                                                        278   63  liquid NMR:                                                                              1.08 (3H, d, J=7.2), 1.49 (3H, s) 1.98 (1H, m),                               2.44-2.76 (2H, m), 3.00 (6H, s), 3.23 (3H, s),                                6.38 (1H, brs), 6.45 (1H, d, J=2.7), 6.50 (1H, dd,                            J=2.7, 9.0), 6.94 (3H, d, J=9.0), 7.32 (2H, d,                                J=9.0).                                                  279   not less                                                                          liquid NMR:                                                                              1.08 (3H, d, J=7.2), 1.78-2.20 (1H, m), 2.36-2.80              than 97        (2H, m), 3.20 (3H, s), 3.24 (3H, s), 3.77 (3H, s),                            6.40-7.56 (7H, m), 7.66 (1H, brs).                       280   93  liquid NMR:                                                                              0.94 (3H, t, J=7.2), 1.25 and 1.36 (total 3H, s),                             1.50-1.80 (2H, m), 1.81-2.10 (2H, m), 3.02 (6H, s),                           3.44 and 3.46 (total 3H, s), 4.40 (1H, brs),                                  6.30 (1H, brs), 6.38 (1H, d, J=2.7), 6.54 (1H, dd,                            J=2.7, 8.1), 6.97 (2H, d, J=8.1), 7.20-7.50 (3H,                              m).                                                      281   88  liquid NMR:                                                                              0.94 (3H, t, J=7.2), 1.24 and 1.34 (total 3H, s),                             1.50-1.80 (2H, m), 3.18 (3H, s), 3.44 and 3.46                                (total 3H, s), 3.76 (3H, s), 4.4 (1H, brs),                                   6.38 (1H, d, J=2.7), 6.54 (1H, dd, J=2.7, 8.1),                               6.98 (2H, d, J=8.1), 7.28 (1H, d, J=8.1),                                     7.42 (2H, d, J=8.1), 7.66 (1H, brs).                     282   90  liquid IR: 3300 (ν.sub.NH), 1640 (ν.sub.c=o).                 283   94  liquid IR: 3400 (ν.sub.NH), 3310 (ν.sub.NH), 1640                                  (ν.sub.c=o).                                          284   80  liquid NMR:                                                                              0.89 (6H, t, J=7.2), 1.50-2.10 (6H, m), 3.03 (6H,                             s),                                                                           3.46 (3H, s), 4.38 (1H, t, J=6.3), 6.26 (1H, brs),                            6.39 (1H, d, J=2.7), 6.54 (1H, dd, J=2.7, 8.1),                               6.98 (2H, d, J=8.1), 7.28 (1H, d, J=8.1), 7.34 (2H,                           d,                                                                            J=8.1).                                                  285   80  liquid NMR:                                                                              0.89 (6H, t, J=7.2), 1.50-2.10 (6H, m), 3.18 (3H,                             s),                                                                           3.46 (3H, s), 3.76 (3H, s), 4.39 (1H, t, J= 6.3),                             6.39 (1H, d, J=2.7), 6.54 (1H, dd, J=2.7, 8.1),                               6.99 (2H, d, J=8.1), 7.30 (1H, d, J=8.1), 7.44 (2H,                           d, J=8.1), 7.68 (1H, brs).                               286   77  63-65                                                               287   43  liquid NMR:                                                                              0.90 (6H, t, J=7.2), 1.00-2.20 (8H, m), 3.03 (6H,                             s),                                                                           3.45 (3H, s), 4.38 (1H, t, J=7.2), 6.26 (1H, brs),                            6.39 (1H, d, J=2.7), 6.52 (1H, dd, J=2.7, 8.1),                               6.97 (2H, d, J=8.1), 7.29 (1H, d, J=8.1), 7.44 (2H,                           d,                                                                            J=8.1).                                                  288   63  liquid NMR:                                                                              0.90 (6H, t, J=7.2), 1.00-2.20 (8H, m), 3.19 (3H,                             s),                                                                           3.46 (3H, s), 3.77 (3H, s), 4.38 (1H, t, J=7.2),                              6.39 (1H, d, J=2.7), 6.52 (1H, dd, J=2.7, 8.1),                               6.98 (2H, d, J=8.1), 7.30 (1H, d, J=8.1), 7.42 (2H,                           d,                                                                            J=8.1), 7.66 (1H, brs).                                  289   57  68-69                                                               290   86  67-68  NMR:                                                                              1.01 (3H, t, J= 7.2), 1.52-2.12 (4H, m), 2.98 (6H,                            s),                                                                           3.92-4.40 (5H, m), 6.44 (1H, dd, J=2.7,9.0),                                  6.59 (1H, d, J=2.7), 6.65 (1H, brs), 6.92 (2H, d,                             J=                                                                            9.0), 7.32 (3H, d, J=9.0).                               291   91  liquid NMR:                                                                              1.03 (3H, t, J=7.2), 1.56-2.20 (4H, m), 3.20 (3H,                             s),                                                                           3.78 (3H, s), 4.00-4.50 (5H, m), 6.39 (1H, d,                                 J=2.7),                                                                       6.57 (1H, dd, J=2.7, 9.0), 7.00 (2H, d, J=9.0),                               7.44 (3H, d, J=9.0), 7.68 (1H, brs).                     292   86  173-175                                                             293   83    78-79.5                                                           294   73  liquid NMR:                                                                              1.00 (6H, d, J=6.3), 1.85-1.94 (3H, m), 3.20 (3H,                             s),                                                                           3.80 (3H, s), 4.02 (1H, m), 4.15 (4H, m), 6.30-6.60                           (3H, m), 6.92 (2H, d, J=9.0), 7.30 (2H, d, J=9.0).       295   85  160-161                                                                              NMR:                                                                              0.97 (3H, d, J=7.0), 1.37 (3H, d, J=7.0), 2.11 (1H,                           m),                                                                           3.02 (6H, s), 4.09-4.35 (5H, m), 6.30 (1H, brs),                              6.35 (1H, d, J=2.7), 6.56 (1H, dd, J=2.7, 9.0),                               6.95 (2H, d, J=9.0), 7.20 (1H, d, J=9.0),                                     7.33 (2H, d, J=9.0).                                     296   not less                                                                          109-110                                                                              NMR:                                                                              0.96 (3H, d, J=7.0), 1.36 (3H, d, J=7.0), 2.11 (1H,                           m),                                                            than 97        3.16 (3H, s), 3.74 (3H, s), 4.08-4.40 (5H, m),                                6.35 (1H, d, J=2.7), 6.51 (1H, dd, J=27, 9.0),                                6.97 (2H, d, J=9.0), 7.20 (1H, d, J=9.0),                                     7.42 (2H, d, J=9.0), 7.71 (1H, brs).                     297   92  77-79                                                               298   92  liquid NMR:                                                                              1.42 (6H, s), 2.13 (2H, s), 3.20 (3H, s), 3.78 (3H,                           s),                                                                           4.00-4.30 (4H, m), 6.38 (1H, d, J=2.7), 6.59 (1H,                             dd,                                                                           J=2.7, 9.0), 7.02 (2H, d, J=9.0), 7.36 (1H, d,                                J=9.0),                                                                       7.50 (2H, d, J=9.0), 7.70 (1H, brs).                     299   80  liquid NMR:                                                                              0.92 (3H, t, J=7.2), 1.33 (3H, s), 1.73 (2H, q,                               J=7.2),                                                                       2.06 (1H, d, J=14.4), 2.26 (1H, d, J=14.4), 2.78                              (3H,                                                                          d, J=5.4), 4.00-4.30 (4H, m), 5.20 (1H, brs), 6.35                            (1H, d, J=2.7), 6.54 (1H, dd, J=2.7, 8.1), 6.98 (2H,                          d,                                                                            J=8.1), 7.20-7.60 (3H, m).                               300   84  liquid NMR:                                                                              0.92 (3H, t, J=7.2), 1.33 (3H, s), 1.73 (2H, q,                               J=7.2),                                                                       2.05 (1H, d, J=14.4), 2.26 (1H, d, J=14.4), 3.00                              (6H,                                                                          s), 4.00-4.30 (4H, m), 6.35 (1H, d, J=2.7), 6.42                              (1H,                                                                          brs), 6.54 (1H, dd, J=2.7, 8.1), 6.98 (2H, q,                                 J=8.1),                                                                       7.20-7.30 (3H, m).                                       301   90  liquid NMR:                                                                              0.92 (3H, t, J=7.2), 1.33 (3H, s), 1.73 (2H, q,                               J=7.2),                                                                       2.03 (1H, d, J=14.4), 2.21 (1H, d, J=14.4), 3.18                              (3H,                                                                          s), 3.74 (3H, s), 4.0-4.3 (4H, m), 6.35 (1H, d, J=                            2.7), 6.54 (1H, dd, J=2.7, 8.1), 6.98 (2H, d,                                 J=8.1),                                                                       6.98 (2H, d, J=8.1), 7.45 (3H, d, J=8.1).                302   80    73- 76.5                                                                           IR: 3320 (ν.sub.NH), 1640 (ν.sub.c=o).                 303   not less                                                                          liquid IR: 3400 (ν.sub.NH), 3325 (ν.sub.NH), 1678                                  (ν.sub.c=o).                                                than 97                                                                 304   80  liquid NMR:                                                                              0.87 (6H, t, J=7.2), 1.68 (4H, q, J=7.2), 2.09 (2H,                           s),                                                                           3.03 (6H, s), 4.00-4.30 (4H, m), 6.24 (1H, brs),                              6.35 (1H, d, J=2.7), 6.54 (1H, dd, J=2.7, 8.1),                               6.96 (2H, d, J=8.1), 7.30 (1H, d, J=8.1), 7.42 (2H,                           d,                                                                            J=8.1).                                                  305   87  liquid NMR:                                                                              0.87 (6H, t, J=7.2), 1.68 (4H, q, J=7.2), 2.09 (2H,                           s),                                                                           3.18 (3H, s), 3.76 (3H, s), 4.00-4.30 (4H, m),                                6.35 (1H, d, J=2.7), 6.54 (1H, dd, J =2.7, 8.1),                              6.96 (2H, d, J=8.1), 7.30 (1H, d, J=8.1), 7.42 (2H,                           d,                                                                            J=8.1), 7.68 (1H, brs).                                  306   83  liquid NMR:                                                                              0.87 (6H, t, J=7.2), 1.68 (4H, q, J= 7.2), 2.08 (2H,                          s),                                                                           2.10-2.50 (2H, m), 2.74 (3H, d, J=4.4), 4.00-4.30                             (4H, m), 5.58 (1H, brs), 6.35 (1H, d, J=2.7), 6.52                            (1H, d, J=2.7, 8.1), 6.98 (2H, d, J=8.1), 7.24 (1H,                           d,                                                                            J=8.1), 7.44 (2H, d, J=8.1), 7.56 (1H, brs).             307   70  182-187                                                             308   75  126-127                                                                              NMR:                                                                              0.88 (6H, t, J=7.2), 1.10-1.50 (2H, m), 1.69 (4H,                             q,                                                                            J=7.2), 2.09 (2H, s), 3.17 (3H, s), 3.72 (3H, s),                             3.90-4.30 (4H, m), 6.35 (1H, d, J=2.7Hz), 6.55 (1H,                           dd, J=2.7, 8.1), 6.98 (2H, d, J=8.1), 7.24 (1H, d,                            J=8.1), 7.44 (2H, d, J=8.1), 7.78 (1H, brs).             309   not less                                                                          liquid NMR:                                                                              1.36 (3H, s), 1.62 (3H, s), 1.68 (1H, s), 1.80 (3H,            than 97        s), 3.02 (6H, s), 6.35 (1H, brs), 6.38 (1H, d,                                J=2.7),                                                                       6.53 (1H, dd, J=2.7, 9.0), 6.94 (2H, d, J=9.0),                               7.09 (1H, d, J=9.0), 7.33 (2H, d, J=9.0).                310   not less                                                                          liquid NMR:                                                                              1.35 (3H, s), 1.61 (3H, s), 1.68 (1H, s), 1.79 (3H,            than 97        s), 3.17 (3H, s), 3.75 (3H, s), 6.38 (1H, d,                                  J=2.7),                                                                       6.52 (1H, dd, J=2.7, 9.0), 6.96 (2H, d, J=9.0),                               7.09                                                                          (1H, d, J=9.0), 7.41 (2H, d, J=9.0), 7.67 (1H,                                brs).                                                    311   not less                                                                          161-162                                                                   than 97                                                                 312   89  40-43  NMR:                                                                              1.80-2.24 (6H, m), 3.01 (6H, s), 3.06 (1H, m),                                3.53 (3H, s), 6.39 (1H, dd, J=2.7, 9.0), 6.43 (1H,                            d,                                                                            J=2.7), 6.52 (1H, brs), 6.88 (1H, d, J=9.0),                                  6.94 (2H, d, J=9.0), 7.34 (2H, d, J=9.0).                313   not less                                                                          liquid NMR:                                                                              1.76-2.30 (6H, m), 3.01 (1H, m), 3.12 (3H, s),                 than 97        3.47 (3H, s), 3.71 (3H, s), 6.26-7.48 (7H, m),                                7.66 (1H, brs).                                          314   93  166-168                                                             315   not less                                                                          58-59                                                                     than 97                                                                 316   89  liquid NMR:                                                                              1.40-1.92 (6H, m), 2.00-2.30 (2H, m), 3.18 (1H, m),                           3.19 (3H, s), 3.38 (3H, s), 3.76 (3H, s), 6.46 (1H,                           dd, J=2.7, 9.0), 6.49 (1H, d, J=2.7), 6.96 (1H, d,                            J=9.0), 7.00 (2H, d, J=9.0), 7.45 (2H, d, J=9.0),                             7.73 (1H, brs).                                          317   97  211-213                                                                              IR: 3330 (ν.sub.NH), 3050 (ν.sub.OH), 1624                                  (ν.sub.c=o).                                                           NMR:                                                                              1.29 (3H, s), 1.47 (3H, s), 1.57 (3H, s), 1.77 (1H,                           d,                                                                            J=14.4), 2.00 (1H, d, J=14.4), 3.09 (3H, s), 5.75                             (1H, brs), 6.28 (1H, d, J=2.7), 6.52 (1H, dd,                                 J=2.7,                                                                        9.0), 6.91 (2H, d, J=9.0), 7.21 (1H, d, J=9.0),                               7.39 (2H, d, J=9.0), 8.13 (1H, brs).                     318   93    190-191.5                                                                          IR: 3350 (ν.sub.NH), 3040 (ν.sub.OH), 1627                                  (ν.sub.c=o).                                                           NMR:                                                                              1.28 (3H, s), 1.46 (3H, s), 1.56 (3H, s), 1.78 (1H,                           d,                                                                            J=14.4), 2.00 (1H, d, J=14.4), 3.03 6H, s), 6.32                              (1H, d, J=2.7), 6.54 (1H, dd, J=2.7, 9.0), 6.92 (2H,                          d,                                                                            J=9.0), 7.19 (1H, d, J=9.0), 7.38 (2H, d, J=9.0).        319   97  137-139                                                                              IR: 3410 (ν.sub.NH), 3050 (ν.sub.OH), 1627                                  (ν.sub.c=o).                                                           NMR:                                                                              1.28 (3H, s), 1.41 (3H, s), 1.56 (3H, s), 1.80 (1H,                           d, J=15.3), 2.02 (1H, d, J=15.3), 3.16 (3H, s),                               3.38 (1H, brs), 3.73 (3H, s), 6.38 (1H, d, J=2.7),                            6.53 (1H, dd, J=2.7, 9.0), 6.95 (2H, d, J=9.0),                               7.20 (1H, d, J=9.0), 7.40 (2H, d, J=9.0), 7.73 (1H,                           brs).                                                    320   72  128.5-130                                                                            NMR:                                                                              1.38 (3H, d, J=7.2), 1.64-2.00 (2H, m), 2.60-2.92                             (2H, m), 3.00 (6H, s), 4.00-4.36 (1H, m), 6.63 (1H,                           brs), 6.70-7.00 (4H, m), 7.90 (1H, dd, J=2.7, 9.0),                           8.01 (1H, d, J=2.7).                                     321   91  93-94  NMR:                                                                              1.39 (3H, d, J=7.2), 1.64-2.00 (2H, m), 2.68-3.00                             (2H, m), 3.20 (3H, s), 3.78 (3H, s), 3.92-4.40                                (1H, m), 6.72-7.00 (4H, m), 7.69 (1H, brs),                                   8.01 (1H, dd, J=2.7, 9.0), 8.14 (1H, d, J=2.7).          322   not less                                                                          180-182                                                                   than 97                                                                 323   95  154-155                                                                              IR: 3335 (ν.sub.NH), 1642 (ν.sub.c=o).                 324   not less                                                                          108-109                                                                              IR: 3310 (ν.sub.NH), 1665 (ν.sub.c=o).                       than 97                                                                 325   not less                                                                          100-102                                                                              NMR:                                                                              1.32 (6H, s), 1.77 (2H, t, J=7.2), 2.73 (2H, t,                               J=7.2),                                                                       3.00 (6H, s), 6.51 (1H, brs), 6.44-6.90 (4H, m),                              7.89 (1H, dd, J=2.7, 9.0), 7.99 (1H, d, J=2.7).          326   78  liquid NMR 1.36 (6H, s), 1.78 (2H, t, J=7.2), 2.75 (2H, t,                               J=7.2),                                                                       3.10 (3H, s), 3.77 (3H, s), 6.67-6.92 (4H, m),                                7.70 (1H, brs), 7.96 (1H, dd, J=2.7, 9.0),                                    8.10 (1H, d, J=2.7).                                     327   75  168-169                                                                              IR: 3285 (ν.sub.NH), 1643 (ν.sub.c=o).                 328   86  106-108                                                                              IR: 3290 (ν.sub.NH), 1667 (ν.sub.c=o).                 329   84  174-176                                                                              IR: 3265 (ν.sub.NH), 1640 (ν.sub.c=o).                 330   not less                                                                            91-92.5                                                                            IR: 3390 (ν.sub.NH), 1686 (ν.sub.c=o).                       than 97                                                                 332   74  171.5-172                                                                            IR: 3280 (ν.sub.NH), 1635 (ν.sub.c=o).                 333   not less                                                                          liquid IR: 3310 (ν.sub.NH), 1672 (ν.sub.c=o).                       than 97                                                                 334   82  191-193                                                                              NMR:                                                                              1.34 (6H, d, J=6.9), 2.68-3.28 (1H, m), 2.80 (3H, d,                          J=                                                                            4.4), 5.02 (1H, brs), 6.30 (1H, s), 6.64-7.60 (8H,                            m).                                                      335   73  153-155                                                                              NMR:                                                                              1.35 (6H, d, J=6.9), 2.98-3.10 (1H, m), 3.04 (6H,                             s),                                                                           6.26 (1H, brs), 6.36 (1H, s), 6.84-7.46 (7H, m).         336   not less                                                                          liquid NMR:                                                                              1.34 (6H, d, J=6.9), 2.86-3.30 (1H, m), 3.16 (3H,                             s),                                                            than 97        3.72 (3H, s), 6.28 (1H, s), 6.88 (1H, dd, J=2.7,                              9.0),                                                                         6.93 (2H, d, J=9.0), 7.10 (1H, d, J=2.7), 7.35 (1H,                           d,                                                                            J=9.0), 7.40 (2H, d, J=9.0), 7.72 (1H, brs).             337   77  137-138                                                                              NMR:                                                                              0.98 (3H, d, J=6.9), 1.02 (3H, d, J=6.9), 1.90-2.28                           (1H, m), 2.64 (2H, dd, J=2.7, 6.7), 3.00 (6H, s),                             6.32 (1H, s), 6.48 (1H, brs), 6.80-7.04 (3H, m),                              7.08 (1H, d, J=2.7), 7.30 (2H, d, J=9.0),                                     7.34 (1H, d, J=9.0).                                     338   86  67-69  NMR:                                                                              0.89 (6H, d, J=6.9), 1.76-2.20 (1H, m), 2.52 (2H,                             d,                                                                            J=6.9), 3.08 (3H, s), 3.64 (3H, s), 6.22 (1H, s),                             6.68-7.50 (7H, m), 7.64 (1H, brs).                       339   80  123-124                                                                              NMR:                                                                              1.28 (3H, t, J=7.7), 2.62 (2H, q, J=7.7), 3.00 (6H,                           s),                                                                           6.44 (1H, brs), 6.80-7.50 (8H, m).                       340   78  liquid IR: 3325 (ν.sub.NH), 1675 (ν.sub.c=o).                 341   not less                                                                          liquid IR: 3325 (ν.sub.NH), 1655 (ν.sub.c=o).                       than 97                                                                 342   68  liquid NMR:                                                                              0.80-1.84 (5H, m), 2.56 (2H, t, J=7.7), 2.95 (6H,                             s),                                                                           6.68-7.50 (9, m).                                        343   83  liquid NMR:                                                                              0.80-1.84 (5H, m), 2.56 (2H, t, J=7.7), 3.16 (3H,                             s),                                                                           3.71 (3H, s), 6.72-7.74 (8H, m), 7.78 (1H, brs).         344   85  liquid NMR:                                                                              1.30 (6H, d, J=6.7), 2.90-3.14 (1H, m), 3.02 (6H,                             s),                                                                           6.48 (1H, brs), 6.70-7.56 (8H, m).                       345   92  liquid NMR:                                                                              1.32 (6H, d, J=6.7), 2.86-3.24 (1H, m), 3.21 (3H,                             s),                                                                           3.78 (3H, s), 6.70-7.56 (8H, m), 7.71 (1H, brs).         346   not less                                                                          liquid NMR:                                                                              1.42 (3H, d, J=6.3), 2.84 (1H, dd, J=7.2, 14.4),                              3.00                                                           than 97        (6H, s), 2.96 (1H, dd, J=7.2, 14.4), 2.92 (1H, m),                            6.66 (1H, brs), 6.68-7.10 (4H, m), 7.80-8.08 (2H,                             m).                                                      347   74  liquid NMR:                                                                              1.42 (3H, d, J=6.3), 2.85 (1H, dd, J=7.2, 14.4),                              3.20 (3H, s), 3.38 (1H, dd, J=7.2, 14.4),                                     3.78 (3H, s), 4.94 (1H, m), 6.72-7.16 (4H, m),                                7.64 (1H, brs), 7.92-8.20 (2H, m).                       348   84  100.5-101.5                                                                          NMR:                                                                              1.47 (3H, d, J=6.4), 2.86 (1H, dd, J=7.7, 15.4),                              3.00 (6H, s), 3.38 (1H, dd, J=7.7, 15.4),                                     5.00 (1H, m), 6.44 (1H, brs), 6.68-6.90 (3H, m),                              6.94 (2H, d, J=9.0), 7.32 (2H, d, J=9.0).                349   87  86-88  NMR:                                                                              1.46 (3H, d, J=6.4), 2.88 (1H, dd, J=7.7, 15.4),                              3.17 (3H, s), 3.40 (1H, dd, J=7.7, 15.4),                                     3.75 (3H, s), 5.00 (1H, m), 6.66-6.96 (3H, m),                                6.97 (2H, d, J=9.0), 7.40 (2H, d, J=9.0),                                     7.64 (1H, brs).                                          350   95  161-162                                                                              IR: 3320 (ν.sub.NH), 3280 (ν.sub.NH), 1635                                  (ν.sub.c=o).                                          351   81  157-158                                                                              IR: 3220 (ν.sub.NH), 1635 (ν.sub.c=o).                 352   81    93-93.5                                                                            IR: 3280 (ν.sub.NH), 1660 (ν.sub.c= o).                353   76  166.5-168                                                                            NMR:                                                                              1.24 (6H, s), 1.79 (2H, t, J=7.1), 2.81 (2H, t,                               J=7.1),                                                                       3.00 (6H, s), 6.33 (1H, brs), 6.74-6.92 (3H, m),                              6.84 (2H, d, J=9.0), 7.26 (2H, d, J=9.0).                354   87    118-119.5                                                                          NMR:                                                                              1.27 (6H, s), 1.80 (2H, t, J=7.1), 2.82 (2H, t,                               J=7.1),                                                                       3.18 (3H, s), 3.76 (3H, s), 6.68-6.96 (3H, m),                                6.88 (2H, d, J=9.0), 7.36 (2H, d, J=9.0),                                     7.64 (1H, brs).                                          355   not less                                                                          190-191                                                                   than 97                                                                 356   77  174-175                                                             357   89  104-105                                                             358   not less                                                                          175.5-176.5                                                               than 97                                                                 359   82  153-155                                                             360   not less                                                                          liquid NMR:                                                                              1.19 (3H, d, J=7.2), 1.37 (3H, s), 1.39 (3H, s),               than 97        2.22 (3H, s), 3.09 (1H, q, J=7.2), 3.20 (3H, s),                              3.77 (3H, s), 6.19 (1H, brs), 6.35 (1H, brs),                                 6.96 (2H, d, J=9.0), 7.43 (2H, d, J=9.0),                                     7.69 (1H, brs).                                          361   not less                                                                          116-117                                                                   than 97                                                                 362   not less                                                                          135-136                                                                   than 97                                                                 363   not less                                                                          liquid NMR:                                                                              0.92 (3H, t, J=7.2), 1.18 (3H, d, J=6.3), 1.30 (3H,                           s),                                                            than 97        1.66 (2H, q, J=7.2), 2.20 (3H, s), 3.12 (1H, q,                               J=6.3),                                                                       3.18 (3H, s), 3.76 (3H, s), 6.15 (1H, brs),                                   6.32 (1H, brs), 6.92 (2H, d, J=9.0),                                          7.39 (2H, d, J=9.0), 7.64 (1H, brs).                     364   65  liquid NMR:                                                                              1.29 (3H, s), 1.80 (2H, t, J=6.7), 2.16 (3H, s),                              2.58 (2H, t, J=6.7), 3.04 (6H, s), 6.26 (1H, d,                               J=2.7), 6.40 (1H, d, J=2.7), 6.96 (2H, d, J=9.0),                             7.32 (2H, d, J=9.0).                                     365   80  liquid NMR:                                                                              1.28 (6H, s), 1.78 (2H, t, J=7.1), 2.16 (3H, s),                              2.56 (2H, t, J=7.1), 3.16 (3H, s), 3.72 (3H, s),                              6.28 (1H, d, J=2.7), 6.40 (1H, d, J=2.7), 6.97 (2H,                           d, J=9.0), 7.42 (2H, d, J= 9.0), 7.76 (1H, brs).         366   not less                                                                          164-165                                                                   than 97                                                                 367   86  181-182                                                             368   not less                                                                          109-111                                                                   than 97                                                                 369   not less                                                                          176-177                                                                   than 97                                                                 370   92    179-180.5                                                         371   88  liquid NMR:                                                                              1.14 (3H, d, J=7.2), 1.52 (3H, s), 1.80-2.12 (1H,                             m),                                                                           2.44 (2H, d, J=9.0), 3.21 (3H, s), 3.24 (3H, s),                              3.79                                                                          (3H, s), 6.33 (1H, d, J=2.1), 6.45 (1H, d, J=2.1),                            7.00                                                                          (2H, d, J=9.0), 7.43 (2H, d, J=9.0), 7.67 (1H,           __________________________________________________________________________                         brs).                                                

The following Formulation Examples are given for the herbicide of thisinvention. All percentages in these examples are by weight.

FORMULATION EXAMPLE 1 Wettable powder

The compound [I] of this invention (10%), 3% of a sodium salt of ahigher alcohol sulfate ester and 87% of kaolin were uniformly mixed andpulverized to form a wettable powder.

FORMULATION EXAMPLE 2 Emulsifiable concentrate

The compound [I] of this invention (20%), 10% of polyoxyethylenealkylaryl ether, 30% of cyclohexanone and 40% of dimethylformamide wereuniformly dissolved to form an emulsifiable concentrate.

FORMULATION EXAMPLE 3 Granules

The compound [I] of this invention (5%), 40% of benzonite, 50% of clayand 5% of sodium ligninsulfonate were uniformly mixed and pulverized.The mixture was kneaded with water, granulated and dried to formgranules.

FORMULATION EXAMPLE 4 Dust

The compound [I] of this invention (3%) and 97% of clay were uniformlymixed and pulverized to form a dust.

The following Test Examples specifically illustrate the herbicide ofthis invention.

TEST EXAMPLE 1 Herbicidal test in upland foliage treatment

Porcelain pots (12 cm in inside diameter) were filled with sieved uplandfarm soil, and seeds of cocklebur, blackjack, velvet leaf, jimsonweed,soybean, wheat, corn and rice were sown and covered with the soil (1cm). They were grown in a greenhouse until the first leaf of soybeandeveloped. A predetermined amount of each of the test compounds,formulated into a wettable powder in accordance with Formulation Example1, was dispersed in 15 liters (per are) of water containing 500 ppm ofNeoesterin as a sticker). The dispersion was sprayed to the leaves andstalks of the plants from the top of the plants by a small atomizer.After the treatment, the plants were grown further in the greenhouse for20 days, Herbicidal effects and phytotoxicity on these plants wereexamined, and evaluated in accordance with the standards shown in Table14. The results are shown in Table 15.

                  TABLE 14                                                        ______________________________________                                        Index       Herbicidal effect and phytotoxicity                               ______________________________________                                        5           more than 99% to 100% (withered)                                  4.5         90% to 99%                                                        4           80% to 89%                                                        3.5         70% to 79%                                                        3           60% to 69%                                                        2.5         50% to 59%                                                        2           40% to 49%                                                        1.5         30% to 39%                                                        1           20% to 29%                                                        0.5          1% to 19%                                                        0           less than 1% (no herbicidal effect, or                                        no phytotoxicity)                                                 ______________________________________                                    

                  TABLE 15                                                        ______________________________________                                        Test      Rate    Herbicidal effect                                                                           Phytotoxicity                                 compound  kg/ha   A     B    C   D    E   F    G   H                          ______________________________________                                        1         2       5     5    3   5    0   0    0   0                                    1       3     5    2   5    0   0    0   0                          2         2       5     5    5   5    0   2    1   2                                    1       5     5    5   5    0   1    0   1                          4         2       5     5    5   5    0   0    0   0                                    1       5     5    5   5    0   0    0   0                          5         2       5     5    5   5    0   0    0   0                                    1       5     5    5   5    0   0    0   0.5                        6         2       5     5    5        0   0    0   0                                    1       5     5    5        0   0    0   0                          7         2       5     5    5   5    0   0.5  0   2                                    1       5     5    5   5    0   0    0   1                          9         2       5     5    5   5    0.5 0.5      2                                    1       5     5    5   5    0   0        0.5                        10        2       5     5    5   5    0   2    0   1.5                                  1       5     5    5   5    0   0    0   1                          11        2       5     5    5   5    0   0    0   0                                    1       5     5    4   5    0   0    0   0                          16        2       5     4.5  5   5    0   2    0   0.5                                  1       5     3    4.5 4.5  0   0    0   0                          20        2       5     5    5   5    0   0        0                                    1       5     5    5   5    0   0        0                          21        2       5     5    5   5    0   0        0                                    1       5     5    1.5 5    0   0        0                          24        2       5     5    5   5    0   0        0                                    1       5     4    2.5 5    0   0        0                          31        2       5     5    5   5    0   0        1                                    1       5     5    5   5    0   0        0.5                        32        2       5     5    5   5    0   0        3                                    1       5     5    5   5    0   0        1                          33        2       5     5    5   5    0   0                                             1       5     5    5   5    0   0                                   35        2       5     5    5   5    0   0        1                                    1       5     5    5   5    0   0        0                          36        2       5     5    5   5        0        1                                    1       5     4.5  5   5        0        1                          39        2       5     5    5   5    0   0        0                                    1       5     5    5   5    0   0        0                          43        2       5     5    5   5    0   0    0   1                                    1       5     5    5   5    0   0    0   0                          44        2       5     5    5   5    0   0    0   1                                    1       5     5    5   5    0   0    0   0                          55        2       5     5    5   5        0    0   0                                    1       5     5    5   5        0    0   0                          56        2       5     5    5   5        0    0   0                                    1       5     5    5   5        0    0   0                          57        2       5     5    5   5    0   0    0   0                                    1       5     5    5   4.5  0   0    0   0                          58        2       5     5    5   5    0   0    0   3                                    1       5     5    5   5    0   0    0   2                          63        2       5     5    5   5    0   0        3.5                                  1       5     5    5   5    0   0        1                          64        2       5     5    5   5        0        1.5                                  1       5     5    5   5        0        1                          65        2       5     5    5   5    0   0                                             1       5     5    5   5    0   0                                   66        2       5     2    5   5    0   0                                             1       5     2    5   5    0   0                                   67        2       5     5    5   5    0   0                                             1       5     5    5   5    0   0                                   68        2       5     5    5   5    0   0                                             1       5     5    5   5    0   0                                   78        2       5     5    5   5    0   1    0   0.5                                  1       5     5    3   5    0   0    0   0                          79        2       5     5    5   5    0   1.5  0.5 2                                    1       5     5    5   5    0   0    0   1                          81        2       5     5    5   5    0   0    0   0.5                                  1       5     5    5   5    0   0    0   0.5                        82        2       5     5    5   5    0   0    0   2                                    1       5     5    5   5    0   0    0   1                          83        2       4     5    5   5    0   0    0.5 2                                    1       2     5    5   5    0   0    0   1                          84        2       5     5    5   5    0   0.5  0   1                                    1       5     5    5   5    0   0    0   0.5                        85        2       3     5    5   5    0   0    0   0                                    1       2     5    5   5    0   0    0   0                          86        2       5     5    5   5    0   0    0   1                                    1       5     5    5   5    0   0    0   1                          90        2       5     5    5   5    0   0                                             1       5     5    5   5    0   0                                   91        2       5     5    5   5    0   0                                             1       5     5    5   5    0   0                                   93        2       5     5    5   5    0   0    0   2                                    1       3     5    5   5    0   0    0   1                          95        2       5     5    5   5    0   0        1                                    1       5     5    5   5    0   0        0                          96        2       5     5    5   5    0   0.5  1   2                                    1       5     5    5   5    0   0    0   1                          98        2       5     4    5   5        0    0   0                                    1       5     3    5   5        0    0   0                          100       2       5     5    5   5    0   0    0   1                                    1       5     5    5   5    0   0    0   0                          101       2       5     5    5   5    0   0    0   0.5                                  1       5     5    5   2    0   0    0   0                          103       2       5     5    5   5    0   0    0   0.5                                  1       5     5    5   5    0   0    0   0                          105       2       5     5    5   5    0   0                                             1       5     5    5   5    0   0                                   106       2       5     5    5   5    0   0                                             1       5     5    5   5    0   0                                   107       2       5     5    5   5    0   0                                             1       5     5    5   5    0   0                                   108       2       5     5    5   5    0   0                                             1       5     5    5   5    0   0                                   110       2       5     5    5   5        0                                             1       5     4    5   5        0                                   111       2       5     5    5   5        0                                             1       5     5    5   5        0                                   113       2       5     5    5   5    0.5 0    0   2                                    1       5     5    5   5    0   0    0   1                          115       2       5     5    5   5    0   0    0   2                                    1       5     4.5  5   5    0   0    0   0.5                        126       2       5     5    5   5        0.5  1   0                                    1       5     5    2.5 5        0    0   0                          127       2       5     5    5   5        1    1.5 0                                    1       2     5    5   5        0    0   0                          129       2       5     5    5   5        0    0   0                                    1       5     5    5   5        0    0   0                          130       2       5     5    5   5        0    0   0                                    1       5     5    5   5        0    0   0                          131       2       5     5    5   5    0   0    0   2                                    1       5     4.5  5   5    0   0    0   1                          132       2       5     5    5   5    0   2    1   1                                    1       5     5    5   5    0   1    0   0.5                        133       2       5     5    5   5    0   0    0   0                                    1       5     5    5   5    0   0    0   0                          134       2       5     5    5   5    0   0    1   1                                    1       5     5    5   5    0   0    0   0                          136       2       5     5    5   5    0   0    0   0                                    1       5     5    5   5    0   0    0   0                          137       2       5     5    5   5        0    0   0                                    1       5     4    5   5        0    0   0                          140       2       5     5    5   5        0.5  0   0                                    1       5     5    5   5        0    0   0                          141       2       5     4.5  5   5        0    0   0                                    1       5     2    5   5        0    0   0                          142       2       5     5    5   5    0            5                                    1       5     5    5   5    0            1                          143       2       5     5    5   5    0            4.5                                  1       5     5    5   5    0            0.5                        144       2       5     5    1   5        0        0.5                                  1       5     5    0.5 5        0        0.5                        145       2       5     5    5   5        0        4.5                                  1       5     4    5   5        0        3                          151       2       5     5    5   5    0   0    0   1                                    1       5     5    5   5    0   0    0   0                          159       2       5     5    5   5    0   0    0   0                                    1       5     5    3   5    0   0    0   0                          160       2       5     5    5   5    0   0        0                                    1       3     5    5   5    0   0        0                          161       2       5     5    5   5    1   1    1   2                                    1       3.5   5    5   5    0   0    0   1                          162       2       5     5    5   5    0        1   1                                    1       3     5    5   5    0        0   0                          164       2       5     5    5   5    0   0    0.5 2                                    1       5     5    5   5    0   0    0   1                          165       2       5     5    5   5    0            1                                    1       5     5    5   5    0            0.5                        169       2       5     5    5        1   0.5  2   2                                    1       5     5    5        0   0    1   1                          170       2       5     5    5   5    0   2    2   2                                    1       5     5    5   5    0   1    1   1                          172       2       5     5    5   5    0   1    0   2                                    1       5     5    5   5    0   0    0   1                          173       2       5     5    5   5    0   1    0   1                                    1       5     5    5   5    0   0    0   0                          174       2       5     5    5   5    0   0    0   0                                    1       3     5    4.5 5    0   0    0   0                          179       2       5     5    5   5    0   0    0   0                                    1       5     5    5   5    0   0    0   0                          180       2       5     5    5        0   0        5                                    1       5     5    5        0   0        3                          181       2       5     5    5        0   0.5      2                                    1       5     5    5        0   0        1                          182       2       5     5    5   5    0   0    0   0                                    1       3     4    5   5    0   0    0   0                          184       2       4     5    5        0   0    0   1                                    1       3     5    5        0   0    0   0                          186       2       5     5    5   5        0    1.5 0                                    1       5     5    5   5        0    0   0                          192       2       5     5    5   5        0    0   0                                    1       4.5   5    5   5        0    0   0                          193       2       5     5    5   5    0   0    0   1                                    1       5     5    5   3    0   0    0   0                          194       2       5     5    5   5    0   0    0   1                                    1       5     5    5   5    0   0    0   0.5                        205       2       5     5    5   5    0   0    0   0                                    1       5     4.5  5   5    0   0    0   0                          206       2       5     5    5   5        0    0   0                                    1       5     5    5   5        0    0   0                          207       2       5     5    5   5        0    0   0                                    1       5     4    5   5        0    0   0                          209       2       5     5    5   5    0   0    0   0                                    1       4.5   4    5   5    0   0    0   0                          210       2       5     5    5   5    1   0    0   1.5                                  1       5     5    5   5    0   0    0   0                          211       2       5     5    5   5    0   0        4.5                                  1       5     5    5   5    0   0        3.5                        212       2       5     5    5   5    0   0        0                                    1       5     3.5  2   5    0   0        0                          220       2       5     5    5   5    0   0        2.5                                  1       5     4.5  2   5    0   0        2                          225       2       5     5    5   5    0   0        1.5                                  1       5     3    5   5    0   0        0                          230       2       5     5    5   5        0        0.5                                  1       2     4.5  5   5        0        0                          232       2       5     5    5   5    0   0        2                                    1       5     5    5   5    0   0        0.5                        233       2       5     5    5   5    0   0        1                                    1       5     5    5   5    0   0        0                          234       2       5     5    5   5    0   0        2                                    1       5     4.5  5   5    0   0        1.5                        235       2       5     3    5   5    0   0        2                                    1       5     3    5   5    0   0        2                          239       2       5     5    5   5    0   0    0   1.5                                  1       5     5    5   5    0   0    0   0                          240       2       5     5    5   5    0   0    0.5 3                                    1       5     5    5   5    0   0    0   2                          244       2       5     5    5   5    0   0    0   0                                    1       5     5    5   5    0   0    0   0                          245       2       4.5   5    5   5    0   0    0   0.5                                  1       3     4    5   5    0   0    0   0                          246       2       5     5    5   5    0   0    0   1                                    1       5     5    5   5    0   0    0   1                          247       2       5     5    5   5    0   0    0   0                                    1       5     5    5   5    0   0    0   0                          248       2       5     5    5   5    0   0    0   0                                    1       5     5    5   5    0   0    0   0                          251       2       5     5    5   5    0   0        4                                    1       5     5    5   5    0   0        2                          252       2       5     5    5   5    0   0                                             1       5     5    5   5    0   0                                   257       2       5     5    5   5        0    0   0                                    1       1.5   5    5   5        0    0   0                          258       2       5     5    5   5    0   2    0   0                                    1       5     5    5   5    0   1    0   0                          260       2       5     4.5  5   5    0   0    0   4.5                                  1       5     1.5  5   5    0   0    0   1                          261       2       5     5    5   5    0   0        3                                    1       5     5    5   5    0   0        1                          262       2       5     5    5   5    0   0        5                                    1       5     5    5   5    0   0        3                          265       2       5     5    5   5    0   1    0   2                                    1       5     2.5  5   5    0   0    0   1                          268       2       5     5    5   5    0   0    0   2                                    1       5     4    5   5    0   0    0   2                          272       2       5     5    5   5    0   0.5  0   4.5                                  1       5     5    5   5    0   0    0   2.5                        273       2       5     5    5   5    0   0.5  0   4.5                                  1       5     5    5   5    0   0    0   4.5                        276       2       5     5    5   5    0   0        2                                    1       5     4    5   5    0   0        1.5                        279       2       5     5    5   5    0   0    1   2                                    1       5     5    5   5    0   0    0   1                          280       2       5     5    5   5    0   0.5  0   4                                    1       5     5    5   5    0   0    0   2.5                        281       2       5     5    5   5    0   0    0   2                                    1       5     4.5  5   5    0   0    0   1                          283       2       5     5    5   5    0   0    0   2                                    1       5     5    5   5    0   0    0   1                          285       2       5     5    5   5    0   0        1.5                                  1       5     5    5   5    0   0        1                          288       2       5     5    5   5    0   0        0.5                                  1       5     5    5   5    0   0        0                          296       2       5     2    5   5    0   0    0   0                                    1       5     2    5   4.5  0   0    0   0                          297       2       5     5    5   5    0   0    0   1.5                                  1       5     5    2   5    0   0    0   1                          309       2       5     4.5  5   5    0   0    0   2                                    1       4.5   4    5   5    0   0    0   2                          310       2       5     5    5   5    0   0    0   1.5                                  1       5     4.5  5   4.5  0   0    0   1                          312       2       5     5    5   5    0   0        4.5                                  1       5     5    5   5    0   0        1                          313       2       5     5    5   5    0   0        3                                    1       5     5    5   5    0   0        0.5                        315       2       5     5    5   5    0   0    0   4                                    1       5     5    5   5    0   0    0   2.5                        316       2       5     5    5   5    0   0    0   3                                    1       5     5    5   5    0   0    0   1                          319       2       5     5    5   5    0   0    0   2                                    1       5     5    5   5    0   0    0   1                          320       2       4     5    5   5    0   2        1.5                                  1       2     5    5   5    0   0    0   1                          321       2       5     5    5   5    0   0    0                                        1       3     5    5   5    0   0    0   1                          323       2       5     5    5   5    0   0    0   0.5                                  1       5     5    5   5    0   0    0   0                          324       2       5     5    5   5    0   0    0   0                                    1       5     5    5   5    0   0    0   0                          326       2       5     5    5        0        0   1.5                                  1       3     4.5  5        0        0   0.5                        327       2       5     5    5   5    0   0    0   0                                    1       5     5    5   5    0   0    0   0                          328       2       5     5    5   5    0   5    1.5 5                                    1       5     5    5   5    0   1    0   0                          330       2       5     5    5   5    0   0    0   2.5                                  1       5     4    5   5    0   0    0   1                          339       2       5     5    5   5    0   0    0   3                                    1       5     3    5   5    0   0    0   2                          340       2       5     4.5  5   5    0   0    0   1                                    1       5     3    5   5    0   0    0   0.5                        343       2       5     2.5  5   5    0   0    0   3                                    1       5     1    5   5    0   0    0   0.5                        344       2       5     5    5   5    0   0        4                                    1       5     5    4.5 5    0   0        3                          345       2       5     3.5  5   5    0   0        4.5                                  1       4.5   3    5   5    0   0        3.5                        348       2       5     5    5   5    0   0    0   3                                    1       5     5    5   5    0   0    0   2                          349       2       5     5    5   5    0   0    0   1                                    1       5     3    5   5    0   0    0   0                          360       2       5     5    5   5    0   0    0   1.5                                  1       5     4.5  5   5    0   0    0   0.5                        362       2       5     5    5   5    0   0    1   2                                    1       4.5   4.5  4.5 2    0   0    0.5 0                          363       2       5     4.5  5   5    0   0    0   1                                    1             3    5   4.5  0   0    0   0.5                        365       2       5     5    5   5    0   0    1   2                                    1       5     5    5   5    0   0    0   2                          371       2       5     5    5   5    0   0    0   2.5                                  1       5     4.5  5   5    0   0    0   1.5                        Comparative                                                                             2       2     3    4   4    2   3    1   2                          Compound (1)                                                                            1       1     1    3   2    1   2    1   2                          Comparative                                                                             2       0     1    1   2    0   0    0   1                          Compound (2)                                                                            1       0     0    0   1    0   0    0   0                          Comparative                                                                             2       4     5    5   4    3   4    3   2                          Compound (3)                                                                            1       2     5    2   3    2   3    2   2                          ______________________________________                                         ##STR523##                                                                    ##STR524##                                                                    ##STR525##                                                               

In Table 15 above and Table 16 given below, the names of the plants areindicated by letters A to J as follows:

A: cocklebur (Xanthium canadense)

B: blackjack (Bidens pilosa)

C: velvet leaf (Abutilon theophrasti)

D: jimsonweed (Datura stramonium)

E: wheat (Triticum aestivum)

F: corn (Zea mays)

G: rice (Oryza sativa)

H: soybean (Glycine max)

I: barnyard grass (Echinochloa crus-galli)

J: Pigweed (Amaranthus retroflexus).

TEST EXAMPLE 2 Herbicidal test by soil treatment

Porcelain pots (9 cm in diameter) were filled with sieved upland farmsoil, and seeds of the plants indicated in Table 16 were sown andcovered with the soil (1 cm). Immediately then, a predetermined amountof a wettable powder of each of the test compounds, prepared as inFormulation Example 1, was diluted with 1.5 ml of water, and thedispersion was uniformly sprayed onto the surface of the soil by a smallatomizer. The plants were grown in a green house for 20 days after thesoil treatment, and the herbicidal effect of each of the test compoundswas examined and evaluated in accordance with the standards shown inTable 14. The results are shown in Table 16.

                  TABLE 16                                                        ______________________________________                                        Test      Rate       Herbicidal effect                                        compound  kg/ha      I     J       B   C                                      ______________________________________                                         7        5          5     5       5   5                                                2.5        4.5   3.5     5   5                                       84       5          5     5       5   5                                                2.5        3     5       4.5 5                                       85       5          2     5       5   5                                                2.5        1     5       4.5 5                                       95       5          4.5   5       4.5 5                                                2.5        1     5       3   5                                       96       5          5     5       5   5                                                2.5        4.5   5       5   5                                      103       5          1     5       5   5                                                2.5        0     5       4   5                                      105       5          0     5       5   5                                                2.5        0     5       2   5                                      113       5          4     5       5   5                                                2.5        1.5   4.5     3   4.5                                    132       5          5     5       5   5                                                2.5        5     5       4.5 5                                      151       5          1     5       5   5                                                2.5        0     5       5   4.5                                    169       5          5     5       5   5                                                2.5        5     3       5   4                                      190       5          4     5       5   5                                                2.5        2     5       5   5                                      191       5          4.5   5       5   5                                                2.5        3     5       5   5                                      194       5          2     5       5   5                                                2.5        0     5       5   5                                      310       5          0     5       5   5                                                2.5        0     5       4.5 4.5                                    319       5          3.5   5       5   5                                                2.5        0     5       5   4.5                                    365       5          1     5       5   5                                                2.5        0     2       5   5                                      ______________________________________                                    

INDUSTRIAL UTILIZABILITY

The compounds of formula [I] of this invention are useful forcontrolling undesired vegetation in low dosages without substantialphytotoxicity on useful crops.

We claim:
 1. A urea derivative represented by the following formula [I]##STR526## wherein A represents the bond ##STR527## in which X is ahydrogen atom, a chlorine atom, a nitro group or a trifluoromethylgroup;B represents a hydrogen atom, a methyl group or a methoxy group;and Ar represents one member selected from the group consisting of##STR528## in which R¹ to R³⁸, independently from each other, representa hydrogen atom, a lower alkyl group or a lower alkoxy group; R¹⁶ mayfurther represent a hydroxyl group; a pair of R² and R³, and a pair ofR⁶ and R⁷ each, taken together, may represent an alkylene linkage andmay form a 5- or 6-membered ring together with the two adjacent carbonatoms to which they are bonded; a pair of R⁹ and R¹⁰, taken together,may represent an alkylene linkage and may form a 5- or 6-membered ringtogether with the carbon atom to which they are bonded; R¹¹ and R¹²,taken together, may form an ethylenedioxy linkage --O--(CH₂)₂ --O--, orR¹¹ and R¹⁵, taken together, may form an alkylene linkage and form a 5-or 6-membered ring together with the carbon atoms to which they arebonded, or R¹⁵ and R¹⁶, taken together, may represent an alkylenelinkage and form a 5- or 6-membered ring together with one carbon atomto which they are bonded, or R¹⁴ and R¹⁵, taken together, may form adichloromethylene linkage.
 2. The urea derivative of claim 1 wherein Xis a hydrogen atom.
 3. The urea derivative of claim 1 wherein X is achlorine atom.
 4. The urea derivative of claim 1 wherein X is a nitrogroup.
 5. The urea derivative of claim 1 wherein X is a trifluoromethylgroup.
 6. The urea derivative represented by the formula [I] as setforth in claim 1 wherein Ar represents one member selected from thegroup (a).
 7. The urea derivative represented by the formula [I] as setforth in claim 1 wherein Ar represents one member selected from thegroup (b).
 8. The urea derivative represented by the formula [I] as setforth in claim 1 wherein Ar represents one member selected from thegroup (c).
 9. The urea derivative represented by the formula [I] as setforth in claim 1 wherein Ar represents one member selected from thegroup (d).
 10. The urea derivative represented by the formula [I] as setforth in claim 1 wherein Ar represents one member selected from thegroup (e).
 11. The urea derivative represented by the formula [I] as setforth in claim 1 wherein Ar represents one member selected from thegroup (f).
 12. The urea derivative represented by the formula [I] as setforth in claim 1 wherein Ar represents one member selected from thegroup (g).
 13. The urea derivative represented by the formula [I] as setforth in claim 1 wherein Ar represents one member selected from thegroup (h).
 14. The urea derivative represented by the formula [I] as setforth in claim 1 wherein Ar represents one member selected from thegroup (i).
 15. The urea derivative represented by the formula [I] as setforth in claim 1 wherein Ar represents one member selected from thegroup (j).
 16. The urea derivative represented by the formula [I] as setforth in claim 1 wherein Ar represents one member selected from thegroup (k).
 17. A herbicidal composition comprising a herbicidallyeffective amount of at least one compound of formula [I] according toclaim 1 and an agriculturally acceptable diluent or carrier.
 18. Theherbicidal composition of claim 17 wherein the amount of the compound offormula [I] is about 0.5 to about 70% by weight based on the weight ofthe composition.
 19. The herbicidal composition of claim 17 which is inthe form of granules or a dust and in which the amount of the compoundof formula [I] is 0.5 to 20% by weight based on the weight of thecomposition.
 20. The herbicidal composition of claim 17 which is in theform of an emulsifiable concentrate or wettable powder and in which theamount of the compound of formula [I] is 5 to 70% by weight based on theweight of the composition.
 21. A method for controlling the growth ofweeds, which comprises applying a herbicidally effective amount of atleast one compound of formula [I] according to claim 1 to the weeds orthe locus of such weeds.
 22. The method for controlling the growth ofweeds according to claim 21 which comprises applying from about 50 g toabout 3 kg/hectare of at least one compound of formula [I] to the weedsor the locus of such weeds.
 23. The method of claim 22 for controllingthe growth of weeds in gramineous crops.
 24. The method of claim 22 forcontrolling the growth of weeds in leguminous crops.